Platinum and rhodium and/or iron containing catalyst formulations for hydrogen generation

ABSTRACT

A method and catalysts for producing a hydrogen-rich syngas are disclosed. According to the method a CO-containing gas contacts a water gas shift (WGS) catalyst, in the presence of water, preferably at a temperature of less than about 450° C. to produce a hydrogen-rich syngas. Also disclosed is a water gas shift catalyst formulated from:  
     a) Pt, its oxides or mixtures thereof,  
     b) at least one of Fe and Rh, their oxides and mixtures thereof, and  
     c) at least one member selected from the group consisting of Sc, Y, Ti, Zr, V, Nb, Ta, Mo, Re, Co, Ni, Pd, Ge, Sn, Sb, La, Ce, Pr, Nd, Sm, and Eu, their oxides and mixtures thereof. The WGS catalyst may be supported on a carrier, such as any one member or a combination of alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, yttria and iron oxide. Fuel processors containing such water gas shift catalysts are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims benefit from earlier filed U.S.Provisional Application No. 60/434,697, filed Dec. 20, 2002, which isincorporated herein in its entirety by reference for all purposes. Thepresent application also incorporates by reference the PCT InternationalPatent Application No. ______ entitled “Platinum and Rhodium and/or IronContaining Catalyst Formulations for Hydrogen Generation” naming asinventors Hagemeyer et al. (Attorney Docket No. 708000501PCT) filed onthe same date as the present application.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] This invention relates to methods and catalysts to generate ahydrogen-rich gas from gas mixtures containing carbon monoxide andwater, such as water-containing syngas mixtures. More particularly, theinvention includes methods using both precious metal- and non-preciousmetal-containing catalysts. The catalysts may be supported on a varietyof catalyst support materials. Catalysts of the invention exhibit bothhigh activity and selectivity to hydrogen generation and carbon monoxideoxidation.

[0004] 2. Discussion of the Related Art

[0005] Numerous chemical and energy-producing processes require ahydrogen-rich composition (e.g. feed stream). A hydrogen-rich feedstream is typically combined with other reactants to carry out variousprocesses. Nitrogen fixation processes, for example, produce ammonia byreacting feed streams containing hydrogen and nitrogen under highpressures and temperatures in the presence of a catalyst. In otherprocesses, the hydrogen-rich feed stream should not contain componentsdetrimental to the process. Fuel cells such as polymer electrodemembrane (PEM) fuel cells, produce energy from a hydrogen-rich feedstream. PEM fuel cells typically operate with a feed stream gas inlettemperature of less than 450° C. Carbon monoxide is excluded from thefeed stream to the extent possible to prevent poisoning of the electrodecatalyst, which is typically a platinum-containing catalyst. See U.S.Pat. No. 6,299,995.

[0006] One route for producing a hydrogen-rich gas is hydrocarbon steamreforming. In a hydrocarbon steam reforming process steam is reactedwith a hydrocarbon fuel, such as methane, iso-octane, toluene, etc., toproduce hydrogen gas and carbon dioxide. The reaction, shown below withmethane (CH₄), is strongly endothermic; it requires a significant amountof heat.

CH₄+2H₂O→4H₂+CO₂

[0007] In the petrochemical industry, hydrocarbon steam reforming ofnatural gas is typically performed at temperatures in excess of 900° C.Even for catalyst assisted hydrocarbon steam reforming the temperaturerequirement is often still above 700° C. See, for example, U.S. Pat. No.6,303,098. Steam reforming of hydrocarbons, such as methane, usingnickel- and gold-containing catalysts and temperatures greater than 450°C. is described in U.S. Pat. No. 5,997,835. The catalyzed process formsa hydrogen-rich gas, with depressed carbon formation.

[0008] One example of effective hydrocarbon steam reforming catalysts isthe Sinfelt compositions which are composed of Pt, a Group 11 metal, anda Group 8-10 metal. Group 11 metals include Cu, Ag and Au while Group8-10 metals include the other noble metals. These catalyst formulationsare well known in the promotion of hydrogenation, hydrogenolysis,hydrocracking, dealkylation of aromatics, and naphtha reformingprocesses. See, for example, U.S. Pat. Nos. 3,567,625 and 3,953,368. Theapplication of catalysts based on the Sinfelt model to water gas shift(“WGS”) reaction, in particular at conditions suitable for lowertemperature WGS applications such as PEM fuel cells, has not beenpreviously reported.

[0009] Purified hydrogen-containing feed streams have also been producedby filtering the gas mixture produced by hydrocarbon steam reformationthrough hydrogen-permeable and hydrogen-selective membranes. See, forexample, U.S. Pat. No. 6,221,117. Such approaches suffer from drawbacksdue to the complexity of the system and slow flow rates through themembranes.

[0010] Another method of producing a hydrogen-rich gas such as a feedstream starts with a gas mixture containing hydrogen and carbon monoxidewith the absence of any substantial amount of water. For instance, thismay be the product of reforming of a hydrocarbon or an alcohol, andselectively removes the carbon monoxide from that gas mixture. Thecarbon monoxide can be removed by absorption of the carbon monoxideand/or by its oxidation to carbon dioxide. Such a process utilizing aruthenium based catalyst to remove and oxidize the carbon monoxide isdisclosed in U.S. Pat. No. 6,190,430.

[0011] The water gas shift reaction is another mechanism for producing ahydrogen-rich gas but from water (steam) and carbon monoxide. Anequilibrium process, the water gas shift reaction, shown below, convertswater and carbon monoxide to hydrogen and carbon dioxide, and viceversa.

H₂O+CO

H₂+CO₂

[0012] Various catalysts have been developed to catalyze the WGSreaction. These catalysts are typically intended for use at temperaturesgreater than 450° C. and/or pressures above 1 bar. For instance, U.S.Pat. No. 5,030,440 relates to a palladium and platinum-containingcatalyst formulation for catalyzing the shift reaction at 550-650° C.See also U.S. Pat. No. 5,830,425 for an iron/copper based catalystformulation.

[0013] Catalytic conversion of water and carbon monoxide under water gasshift reaction conditions has been used to produce hydrogen-rich andcarbon monoxide-poor gas mixtures. Existing WGS catalysts, however, donot exhibit sufficient activity at a given temperature to reachthermodynamic equilibrium concentrations of hydrogen and carbon monoxidesuch that the product gas may subsequently be used as a hydrogen feedstream. Specifically, existing catalyst formulations are notsufficiently active at low temperatures, that is, below about 450° C.See U.S. Pat. No. 5,030,440.

[0014] Platinum (Pt) is a well-known catalyst for both hydrocarbon steamreforming and water gas shift reactions. Under typical hydrocarbon steamreforming conditions, high temperature (above 850° C.) and high pressure(greater than 10 bar), the WGS reaction may occur post-reforming overthe hydrocarbon steam reforming catalyst due to the high temperature andgenerally unselective catalyst compositions. See, for instance, U.S.Pat. Nos. 6,254,807, 5,368,835, 5,134,109, and 5,030,440 for a varietyof catalyst compositions and reaction conditions under which the watergas shift reaction may occur post-reforming.

[0015] Metals such as cobalt (Co), ruthenium (Ru), palladium (Pd),rhodium (Rh) and nickel (Ni) have also been used as WGS catalysts butare normally too active for the selective WGS reaction and causemethanation of CO to CH₄ under typical reaction conditions. In otherwords, the hydrogen produced by the water gas shift reaction is consumedas it reacts with the CO present in the presence of such catalysts toyield methane. This methanation reaction activity has limited theutility of metals such as Co, Ru, Pd, Rh and Ni as water gas shiftcatalysts.

[0016] A need exists, therefore, for a method to produce a hydrogen-richsyngas, and catalysts which are highly active and highly selective forboth hydrogen generation and carbon monoxide oxidation at moderatetemperatures (e.g. below about 450° C.) to provide a hydrogen-richsyngas from a gas mixture containing hydrogen and carbon monoxide.

SUMMARY OF THE INVENTION

[0017] The invention meets the need for highly active and selectivecatalysts for the generation of hydrogen and the oxidation of carbonmonoxide and to thereby provide a hydrogen-rich gas, such as ahydrocarbon-rich syngas, from a gas mixture of at least carbon monoxideand water. Accordingly, the invention provides methods and catalysts forproducing a hydrogen-rich gas.

[0018] The invention is, in a first general embodiment, a method forproducing a hydrogen-rich gas (e.g., syngas) by contacting aCO-containing gas, such as a syngas mixture with a water gas shiftcatalyst in the presence of water at a temperature of not more than 450°C. In the first general embodiment, the water gas shift catalystcomprises a) Pt, its oxides or mixtures thereof; b) at least one of Feand Rh, their oxides, and mixtures thereof, and c) at least one memberselected from the group consisting of Sc, Y, Ti, Zr, V, Nb, Ta, Mo, Re,Co, Ni, Pd, Ge, Sn, Sb, La, Ce, Pr, Nd, Sm, and Eu, their oxides andmixtures thereof.

[0019] In one preferred embodiment, the water gas shift catalystcomprises Pt, its oxides and mixtures thereof, Rh, its oxides andmixtures thereof, and at least one member selected from the groupconsisting of Ti, Zr, Mo, Co, Ge, Sb, La, and Ce, their oxides, andmixtures thereof. In another preferred embodiment, the water gas shiftcatalyst comprises Pt, its oxides and mixtures thereof, Rh, its oxidesand mixtures thereof, Fe, its oxides and mixtures thereof, and at leastone member selected from the group consisting of Co, Pd, Ge, Sb, La, andCe, their oxides and mixtures thereof. The catalyst may be supported ona carrier, for example, at least one member selected from the groupconsisting of alumina, zirconia, titania, ceria, magnesia, lanthania,niobia, zeolite, perovskite, silica clay, yttria and iron oxide andmixtures thereof. The method of the invention may be conducted at atemperature ranging from about 150° C. to about 450° C.

[0020] In a second general embodiment, the invention relates to thewater gas shift catalysts themselves—both supported and unsupportedcatalysts. The inventive water gas shift catalyst comprises, in a first,general embodiment, Pt, its oxides and mixtures thereof, at least one ofFe and Rh, their oxides, and mixtures thereof, and at least one memberselected from the group consisting of Na, K, Sc, Y, Ti, Zr, V, Nb, Ta,Mo, Re, Co, Ni, Pd, Ge, Sn, Sb, La, Ce, Pr, Nd, Sm, and Eu, their oxidesand mixtures thereof. The catalyst may be supported on a carriercomprising at least one member selected from the group consisting ofalumina, zirconia, titania, ceria, magnesia, lanthania, niobia, yttriaand iron oxide and mixtures thereof.

[0021] In a third general embodiment, the invention is directed to theaforementioned water gas shift catalysts of the second generalembodiment in an apparatus for generating a hydrogen gas containingstream from a hydrocarbon or substituted hydrocarbon feed stream. Theapparatus further comprises, in addition to the WGS catalyst, a fuelreformer, a water gas shift reactor, and a temperature controller. Sucha specific WGS apparatus may be located within another larger apparatus,either stationary or otherwise, for generating energy, or a desiredproduct or feed stream, either gaseous or liquid.

[0022] The following described preferred embodiments of the WGS catalystcan be used in each one of the first, second, and third generalembodiments or in specific, related embodiments (e.g., fuel cellreactors, fuel processors, hydrocarbon steam reformers.)

[0023] In one preferred embodiment the water gas shift catalystcomprises Pt, its oxides and mixtures thereof, Rh, its oxides andmixtures thereof, and at least one member selected from the groupconsisting of Ti, Zr, Mo, Co, Ge, Sb, La, and Ce, their oxides andmixtures thereof.

[0024] In a second preferred embodiment the water gas shift catalyst maybe formulated from Pt, its oxides and mixtures thereof, Rh, its oxidesand mixtures thereof, Fe, its oxides and mixtures thereof, and at leastone of Co, Pd, Ge, Sb, La, and Ce, their oxides and mixtures thereof.

[0025] A person of skill in the art will understand and appreciate thatwith respect to each of the preferred catalyst embodiments as describedin the preceding paragraphs, the particular components of eachembodiment can be present in their elemental state, or in one or moreoxide states, or mixtures thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The patent or application file contains at least one drawingexecuted in color. Copies of this patent or patent applicationpublication with color drawing(s) will be provided by the Office uponrequest and payment of the necessary fee.

[0027] The accompanying drawings, which are included to provide afurther understanding of the invention and are incorporated in andconstitute a part of this specification, illustrate preferredembodiments of the invention and together with the detailed descriptionserve to explain the principles of the invention. In the drawings:

[0028]FIGS. 1A-1D, illustrate the process of producing a library testwafer, and

[0029]FIGS. 1E-1I, illustrate SpotFire plots of the CO conversion versusCO₂ production for the wafer under WGS conditions at varioustemperatures. The legend for FIG. 1A also applies to FIGS. 1B, 1C, and1D exclusively.

[0030]FIGS. 2A-2G illustrate the process of producing a library testwafer. The legend for FIG. 2A also applies to FIGS. 2B-2G exclusively.

[0031]FIGS. 3A-3F illustrate the process of producing a library testwafer. The legend for FIG. 3A also applies to FIGS. 3B-3F exclusively.

[0032]FIGS. 4A-4C illustrate the process of producing a library testwafer, and

[0033]FIGS. 4D-4H, illustrate SpotFire plots of the CO conversion versusCO₂ production for the wafer under WGS conditions at varioustemperatures.

[0034]FIGS. 5A-5I illustrate the process of producing a library testwafer, and

[0035]FIGS. 5J-5L, illustrate SpotFire plots of the CO conversion versusCO₂ production for the wafer under WGS conditions at varioustemperatures. The legend for FIG. 5A also applies to FIGS. 5B-5Gexclusively.

[0036]FIGS. 6A-6F, illustrate the process of producing a library testwafer and

[0037]FIGS. 6G, 6H, and 6I, illustrate SpotFire plots of the COconversion versus CO₂ production for the wafer under WGS conditions atvarious temperatures. The legend for FIG. 6A also applies to FIGS. 6B-6Fexclusively.

[0038]FIG. 7 illustrates plots of CO concentration versus temperaturefor scaled-up catalyst samples under WGS conditions.

[0039]FIGS. 8A-8F, illustrate the compositional make-up of variousexemplary library test wafers. The legend for FIGS. 8A-8C applies onlyto FIGS. 8A-8C. The legend for FIGS. 8D-8F applies only to FIGS. 8D-8F.

[0040]FIG. 9A illustrates a representative plot of CO conversion versusCO₂ production for a prototypical library test wafer at varioustemperatures,

[0041]FIG. 9B illustrates the effect of catalyst selectivity andactivity versus the WGS mass balance, and

[0042]FIG. 9C illustrates the effect of temperature on catalystperformance under WGS conditions.

[0043]FIGS. 10A-10C illustrate plots of CO concentration versustemperature for scaled-up catalyst samples under WGS conditions.

[0044]FIGS. 11A-11B illustrate plots of CO concentration versustemperature for scaled-up catalyst samples under WGS conditions.

DETAILED DESCRIPTION OF THE INVENTION

[0045] The invention relates to a method for producing a hydrogen-richgas, such as a hydrogen-rich syngas. According to the method aCO-containing gas such as a syngas contacts a water gas shift catalyst,in the presence of water, preferably a stoichiometric excess of water,preferably at a temperature of less than about 450° C. to produce ahydrogen-rich gas such as a hydrogen-rich syngas. The reaction pressureis preferably not more than about 10 bar. The invention also relates toa water gas shift catalyst itself and to apparatus such as water gasshift reactors and fuel processing apparatus comprising such WGScatalysts.

[0046] A water gas shift catalyst according to the invention comprises:

[0047] a) Pt, its oxides or mixtures thereof;

[0048] b) at least one of Fe and Rh, their oxides and mixtures thereof;and

[0049] c) at least one member selected from the group consisting of Na,K, Sc, Y, Ti, Zr, V, Nb, Ta, Mo, Re, Co, Ni, Pd, Ge, Sn, Sb, La, Ce, Pr,Nd, Sm, and Eu, their oxides and mixtures thereof. The WGS catalyst maybe supported on a carrier, such as any one member or a combination ofalumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite,perovskite, silica clay, yttria and iron oxide.

[0050] In one preferred embodiment, the water gas shift catalyst may becomprised of Pt, its oxides and mixtures thereof, Rh, its oxides andmixtures thereof, and at least one member selected from the groupconsisting of Ti, Zr, Mo, Co, Ge, Sb, La, and Ce, their oxides andmixtures thereof. In another preferred embodiment, the water gas shiftcatalyst may be comprised of Pt, its oxides and mixtures thereof, Rh,its oxides and mixtures thereof, Fe, its oxides and mixtures thereof,and at least one member selected from the group consisting of Co, Pd,Ge, Sb, La, and Ce, their oxides and mixtures thereof.

[0051] The catalyst may be supported on a carrier, for example, at leastone member selected from the group consisting of alumina, zirconia,titania, ceria, magnesia, lanthania, niobia, yttria and iron oxide andmixtures thereof. The method of the invention may be conducted at atemperature ranging from about 150° C. to about 450° C.

[0052] The WGS catalysts of the invention comprise combinations of atleast three metals or metalloids, selected from at least three groupsa), b), and c) indicated above, in each and every possible permutationand combination, except as specifically and expressly excluded. Althoughparticular subgroupings of preferred combinations of metals ormetalloids are also presented, the present invention is not limited tothe particularly recited subgroupings.

[0053] Discussion regarding the particular function of variouscomponents of catalysts and catalyst systems is provided herein solelyto explain the advantage of the invention, and is not limiting as to thescope of the invention or the intended use, function, or mechanism ofthe various components and/or compositions disclosed and claimed. Assuch, any discussion of component and/or compositional function is made,without being bound by theory and by current understanding, unless andexcept such requirements are expressly recited in the claims. Generally,for example, and without being bound by theory, the metals, Pt,component a), and Fe and Rh, component b), have activity as WGScatalysts. The metals or metalloids of component c) may themselves haveactivity as WGS catalysts, such as Co, but function in combination withPt and one of Fe and Rh to impart beneficial properties to the catalystof the invention.

[0054] Catalysts of the invention can catalyze the WGS reaction atvarying temperatures, avoid or attenuate unwanted side reactions such asmethanation reactions, as well as generate a hydrogen-rich gas, such asa hydrogen-rich syngas. The composition of the WGS catalysts of theinvention and their use in WGS reactions are discussed below.

[0055] 1. Definitions

[0056] Water gas shift (“WGS”) reaction: Reaction which produceshydrogen and carbon dioxide from water and carbon monoxide, and viceversa:

H₂O+CO

H₂+CO₂

[0057] Generally, and unless explicitly stated to the contrary, each ofthe WGS catalysts of the invention can be advantageously applied both inconnection with the forward reaction as shown above (i.e., for theproduction of H₂), or alternatively, in connection with the reversereaction as shown above (i.e., for the production of CO). As such, thevarious catalysts disclosed herein can be used to specifically controlthe ratio of H₂ to CO in a gas stream.

[0058] Methanation reaction: Reaction which produces methane and waterfrom a carbon source, such as carbon monoxide or carbon dioxide, andhydrogen:

CO+3H₂→CH₄+H₂O

CO₂+4H₂→CH₄+2H₂O

[0059] “Syngas” (also called synthesis gas): Gaseous mixture comprisinghydrogen (H₂) and carbon monoxide (CO) which may also contain other gascomponents such as carbon dioxide (CO₂), water (H₂O), methane (CH₄) andnitrogen (N₂).

[0060] LTS: Refers to “low temperature shift” reaction conditions wherethe reaction temperature is less than about 250° C., preferably rangingfrom about 150° C. to about 250° C.

[0061] MTS: Refers to “medium temperature shift” reaction conditionswhere the reaction temperature ranges from about 250° C. and up to about350° C.

[0062] HTS: Refers to “high temperature shift” reaction conditions wherethe reaction temperature is more than about 350° C. and up to about 450°C.

[0063] Hydrocarbon: Compound containing hydrocarbon, carbon, and,optionally, oxygen.

[0064] The Periodic Table of the Elements is based on the present IUPACconvention, thus, for example, Group 8 comprises Fe, Ru, and Os. (Seehttp://www.iupac.org dated May 30, 2002.)

[0065] As discussed herein, the catalyst composition nomenclature uses adash (i.e., “-”) to separate catalyst component groups where a catalystmay contain one or more of the catalyst components listed for eachcomponent group, brackets (i.e., “{ }”) are used to enclose the membersof a catalyst component group, “{two of . . . }” is used if two or moremembers of a catalyst component group are required to be present in acatalyst composition, “blank” is used with the “{ }” to indicate thepossible choice that no additional element is added, and a slash (i.e.,“/”) is used to separate supported catalyst components from theirsupport material, if any. Additionally, the elements within catalystcomposition formulations include all possible oxidation states,including oxides, or salts, or mixtures thereof.

[0066] Using this shorthand nomenclature in this specification, forexample, “Pt—{Rh, Ni}—{Na, K, Fe, Os}/ZrO₂” would represent catalystcompositions containing Pt, one or more of Rh and Ni, and one or more ofNa, K, Fe, and Os supported on ZrO₂; all of the catalyst elements may bein any possible oxidation state, unless explicitly indicated otherwise.“Pt—Rh—Ni— {two of Na, K, Fe, Os}” would represent a supported orunsupported catalyst composition containing Pt, Rh, and Ni, and two ormore of Na, K, Fe, and Os. “Rh—{Cu,Ag,Au}—{Na, K, blank}/TiO₂” wouldrepresent TiO₂ supported catalyst compositions containing Rh, one ormore of Cu, Ag and Au, and, optionally, one or more of Na or K.

[0067] 2. WGS Catalyst

[0068] A water gas shift catalyst of the invention comprises:

[0069] a) Pt, its oxides or mixtures thereof;

[0070] b) at least one of Fe and Rh, their oxides and mixtures thereof;and

[0071] c) at least one member selected from the group consisting of Na,K, Sc, Y, Ti, Zr, V, Nb, Ta, Mo, Re, Co, Ni, Pd, Ge, Sn, Sb, La, Ce, Pr,Nd, Sm, and Eu, their oxides and mixtures thereof. Suitable carriers forsupported catalysts are discussed below.

[0072] The catalyst components are typically present in a mixture of thereduced or oxide forms; typically one of the forms will predominate inthe mixture. A WGS catalyst of the invention may be prepared by mixingthe metals and/or metalloids in their elemental forms or as oxides orsalts to form a catalyst precursor. This catalyst precursor mixturegenerally undergoes a calcination and/or reductive treatment, which maybe in-situ (within the reactor), prior to use as a WGS catalyst. Withoutbeing bound by theory, the catalytically active species are generallyunderstood to be species which are in the reduced elemental state or inother possible higher oxidation states. The catalyst precursor speciesare believed to be substantially completely converted to thecatalytically active species by the pre-use treatment. Nonetheless, thecatalyst component species present after calcination and/or reductionmay be a mixture of catalytically active species such as the reducedmetal or other possible higher oxidation states and uncalcined orunreduced species depending on the efficiency of the calcination and/orreduction conditions.

[0073] A. Catalyst Compositions

[0074] As discussed above, one embodiment of the invention is a catalystfor catalyzing the water gas shift reaction (or its reverse reaction).According to the invention, a WGS catalyst may have the followingcomposition:

[0075] a) Pt, its oxides or mixtures thereof;

[0076] b) at least one of Fe and Rh, their oxides and mixtures thereof;and

[0077] c) at least one member selected from the group consisting of Na,K, Sc, Y, Ti, Zr, V, Mo, Re, Co, Ni, Pd, Ge, Sn, Sb, La, Ce, Pr, Nd, Sm,and Eu, their oxides and mixtures thereof. The amount of each componentpresent in a given catalyst according to the present invention may varydepending on the reaction conditions under which the catalyst isintended to operate. Generally, a Group 8, 9 or 10 metal component maybe present in an amount ranging from about 0.01 wt. % to about 10 wt. %,preferably about 0.01 wt. % to about 2 wt. %, and more preferably about0.05 wt. % to about 0.5 wt. %. The lanthanide elements may be present,typically, in amounts ranging from about 0.05 wt. % to about 20 wt. %,preferably about 0.1 wt. % to about 15 wt. %. The main group andmetalloid elements may be present in amounts ranging, generally, fromabout 0.01 wt. % to about 15 wt. %, preferably about 0.02 wt. % to about10 wt. %.

[0078] The above weight percentages are calculated on the total weightof the catalyst component in its final state in the catalyst compositionafter the final catalyst preparation step (i.e., the resulting oxidationstate or states) with respect to the total weight of all catalystcomponents plus the support material, if any. The presence of a givencatalyst component in the support material and the extent and type ofits interaction with other catalyst components may effect the amount ofa component needed to achieve the desired performance effect.

[0079] Other WGS catalysts which embody the invention are listed below.Utilizing the shorthand notation discussed above, where each metal maybe present in its reduced form or in a higher oxidation state, thefollowing compositions are examples of preferred catalyst compositions:

Pt—Rh—{Ge, Sb}.

Pt—Rh—Mo.

Pt—Rh—Co—{La, Ce}.

Pt—Rh—{Ti, Zr, Ce}.

Pt—{Rh, Fe}—{Ge, Sb}.

Pt—{Rh, Fe}—{Co, La, Ce}.

Pt—{Rh, Fe}—Pd.

[0080] Some catalysts may be more advantageously applied in specificoperating temperature ranges. For instance, Pt—Rh—Fe—SbGe andPt—Rh—{Ce,Ti} provide high activity in the HTS temperature range; otherformulations that are particularly preferred for HTS temperatureconditions are Pt—Rh—{Ti, Zr}; Pt—Rh—{Ce,Zr}; and Pt—Rh—Fe—{La,Ce,Co}.

[0081] B. Catalyst Component a): Pt

[0082] A first component in a catalyst of the invention is Pt, componenta). Pt, like all metal components, may be present in a combination ofits reduced forms and its oxides. Catalysts of the invention may containmixtures of these metal states.

[0083] Pt is known to catalyze the WGS reaction. Typically Pt alone istoo active and unselective towards the formation of hydrogen undertypical WGS conditions. However, as demonstrated here, properly modifiedPt containing catalyst formulations may provide both increasedselectivity to hydrogen generation at high activity levels under WGSreaction conditions.

[0084] C. Catalyst Component b): Fe and/or Rh

[0085] Rhodium and other metals including, for instance, ruthenium,cobalt, palladium, and nickel have been used as WGS catalysts but arenormally too active for the selective WGS reaction and cause methanationof CO to CH₄ under typical WGS reaction conditions. In other words, thehydrogen produced by the water gas shift reaction is consumed as itreacts with the CO present in the presence of such catalysts to yieldmethane. This methanation reaction activity has limited the utility ofsuch metals as water gas shift catalysts.

[0086] Unmodified Rh has been shown to catalyze the methanation reactionunder WGS conditions. However, according to the present invention, Rhmay be converted to a highly active and selective WGS catalyst byadjusting the Rh loading and alloying with other catalyst componentswhich may moderate the activity of Rh for the methanation reaction. Inone preferred combination, Pt was found to efficiently alter theselectivity of unmodified Rh. According to the present invention,various dopants may be added to the Pt and Rh containing catalystformulations and some preferred catalysts include, for example,Pt—Rh—Pd, Pt—Rh—Pd—Fe, Pt—Rh—Fe and Pt—Rh—Fe—{Ge,Sb}. The resultingcatalyst compositions are highly active and selective WGS catalysts, andexhibit increased selectivity for the WGS reaction over the competingmethanation reaction.

[0087] Pt—Rh compositions can also be gradually moderated, whileenhancing WGS selectivity at the expense of activity, by addingadditional catalyst components such as, for instance, main group metals,rare earth metals and lanthanides.

[0088] Iron itself is recognized as a selective HTS conventional syngascatalyst but, typically needing temperature in excess of 400° C., is notactive enough for most desired applications. Iron does not reduce to themetal state in the presence of water but stays in an oxidized state.Hence, doping iron with noble metals, preferably Pt or Rh, maintains theselectivity while increasing the activity. Adding Ru tends to provide aless selective composition in contrast to the Pt—Fe or Rh—Fecompositions. Pt—Rh—Fe tends to provide high activity and selectivityunder WGS reaction conditions.

[0089] D. Catalyst Component c): “Functional” Metals or Metalloids

[0090] The WGS catalysts of the invention comprise at least three metalsor metalloids. In addition to the first two components, discussed above,a WGS catalyst comprises metals or metalloids which, when used incombination with Pt, its oxides and mixtures thereof, and at least oneof Fe and Rh, their oxides and mixtures thereof, function to impartbeneficial properties to the catalyst of the invention. A catalyst ofthe invention, then, further comprises at least one member of Sc, Y, Ti,Zr, V, Nb, Ta, Mo, Re, Co, Ni, Pd, Ge, Sn, Sb, La, Ce, Pr, Nd, Sm, andEu, their oxides, and mixtures thereof, component c).

[0091] Pt—Rh containing catalysts may further include activity- orselectivity-enhancing promoters such as Ti, Zr, Mo, Co, Ge, Sb, La, andCe, their oxides and mixtures thereof Preferred carriers include, forinstance, zirconia, ceria and titania. One preferred supported catalystincludes, for example, Pt—Rh—Mo on ZrO₂.

[0092] Pt—Rh—Fe containing catalyst compositions may preferably furthercomprise one or more of Co, Pd, Ge, Sb, La, and Ce, their oxides andmixtures thereof.

[0093] E. Functional Classification of Catalyst Components

[0094] Without limiting the scope of the invention, discussion of thefunctions of the various catalyst components is offered, along with atemplate for composing catalyst compositions according to the invention.The following classification of catalyst components will direct one ofskill in the art in the selection of various catalyst components toformulate WGS catalyst compositions according to the present inventionand depending on the reaction conditions of interest.

[0095] Furthermore, according to the invention, there are severalclasses of catalyst components and metals which may be incorporated intoa water gas shift catalyst. Hence, the various elements recited ascomponents in any of the described embodiments (e.g., as component (c)),may be included in any various combination and permutation to achieve acatalyst composition that is coarsely or finely tuned for a specificapplication (e.g. including for a specific set of conditions, such as,temperature, pressure, space velocity, catalyst precursor, catalystloading, catalyst surface area/presentation, reactant flow rates,reactant ratios, etc.). In some cases, the effect of a given componentmay vary with the operating temperature for the catalyst. These catalystcomponents may function as, for instance, activators or moderatorsdepending upon their effect on the performance characteristics of thecatalyst. For example, if greater activity is desired, an activator maybe incorporated into a catalyst, or a moderator may be replaced by atleast one activator or, alternatively, by at least one moderator onestep further up the “activity ladder.” An “activity ladder” rankssecondary or added catalyst components, such as activators ormoderators, in order of the magnitude of their respective effect on theperformance of principal catalyst constituent. Conversely, if WGSselectivity of a catalyst needs to be increased (e.g., decrease theoccurrence of the competing methanation reaction), then either anactivator may be removed from the catalyst or, alternatively, thecurrent moderator may be replaced by at least one moderator one stepdown the “activity ladder.” The function of these catalyst component maybe further described as “hard” or “soft” depending on the relativeeffect obtained by incorporating a given component into a catalyst. Thecatalyst components may be metals, metalloids, or even non-metals.

[0096] For instance, typically, a WGS catalyst according to theinvention suitable for use under LTS conditions employs activators andmay only be minimally moderated, if at all, because activation isgenerally the important parameter to be considered under LTS conditions.Such LTS catalysts also may preferably employ high surface area carriersto enhance catalyst activity. Conversely, WGS catalysts used in HTSconditions may benefit from the catalyst being moderated becauseselectivity and methanation are parameters to be considered. Such HTScatalysts may use, for example, low surface area carriers. Accordingly,operating temperature may be considered in selecting a WGS catalystaccording to the present invention for a particular operatingenvironment.

[0097] Activators according to the present invention may include Pd andCo as active and selective WGS-promoting metals. Activators may include,but are not limited to, Ti, Zr, V, Mo, La and Ce. Ce may be the mostactive rare earth metal for activating the WGS reaction. La, Pr, Sm andEu may also be active, particularly at lower temperatures. For HTS, Prand Sm are preferred soft moderators enhancing selectivity withoutsacrificing much activity. For LTS, La and Eu may be useful activators.In general, all lanthanides, other than Ce, show comparable performanceand tend to moderate rather than activate noble metal containingcatalyst systems. Y is a highly selective moderator for HTS systemswhereas La and Eu are active and comparable to Ce for LTS. La is onlyslightly moderating when doping Ce and may therefore be used to adjustthe selectivity of Ce containing catalyst systems.

[0098] Catalyst components that are slightly moderating and highlyselective over a broad temperature range (e.g., a temperature range ofat least about 50° C., preferably at least about 75° C., and mostpreferably a temperature range of at least about 100° C.), where suchtemperature range is included within the overall preferred temperatureranges of up to about 450° C. include Y, Mo, Fe, Pr and Sm; these tendto be selective but not very active at low temperatures, about 250° C.The redox dopants Mo, Fe, Pr and Sm generally lose activity withincreasing pre-reduction temperatures while Fe becomes moderately activeon its own at high WGS reaction temperatures.

[0099] Moderators may also include Ge, Sn and Sb. Typically, formoderators to exert a moderating function, they should be substantiallyin the reduced or metallic state. Ge alloyed with Sn is an example of analloy that was found to be highly active, even for low temperaturesystems, when in the fully oxidized state that is when treated at apre-reduction temperature of about 300° C. which reduces the noblemetals selectively but does not change the active oxidized state of theredox dopants.

[0100] F. Supports

[0101] The support or carrier may be any support or carrier used withthe catalyst which allows the water gas shift reaction to proceed. Thesupport or carrier may be a porous, adsorptive, high surface areasupport with a surface area of about 25 to about 500 m²/g. The porouscarrier material may be relatively inert to the conditions utilized inthe WGS process, and may include carrier materials that havetraditionally be utilized in hydrocarbon steam reforming processes, suchas, (1) activated carbon, coke, or charcoal; (2) silica or silica gel,silicon carbide, clays, and silicates including those syntheticallyprepared and naturally occurring, for example, china clay, diatomaceousearth, fuller's earth, kaolin, etc.; (3) ceramics, porcelain, bauxite;(4) refractory inorganic oxides such as alumina, titanium dioxide,zirconium oxide, magnesia, etc.; (5) crystalline and amorphousaluminosilicates such as naturally occurring or synthetically preparedmordenite and/or faujasite; and, (6) combinations of these groups.

[0102] When a WGS catalyst of the invention is a supported catalyst, thesupport utilized may contain one or more of the metals (or metalloids)of the catalyst. The support may contain sufficient or excess amounts ofthe metal for the catalyst such that the catalyst may be formed bycombining the other components with the support. Examples of suchsupports include ceria which can contribute cerium, Ce, (component c))to a catalyst, or iron oxide which can contribute iron, Fe, (componentb)). When such supports are used the amount of the catalyst component inthe support typically may be far in excess of the amount of the catalystcomponent needed for the catalyst. Thus the support may act as both anactive catalyst component and a support material for the catalyst.Alternatively, the support may have only minor amounts of a metal makingup the WGS catalyst such that the catalyst may be formed by combiningall desired components on the support.

[0103] Carrier screening with catalysts containing Pt as the only activenoble metal revealed that a water gas shift catalyst may also besupported on a carrier comprising alumina, zirconia, titania, ceria,magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttriaand iron oxide. Perovskite may also be utilized as a support for theinventive catalyst formulations.

[0104] Zirconia, titania and ceria may be supports for the presentinvention and provide high activity for the WGS reaction. Preferably,zirconia is in the monoclinic phase. Niobia, yttria and iron oxidecarriers provide high selectivity but are also less active which isbelieved to be due to a lack of surface area. Pt on magnesia carriersformulated to have high surface areas (approximately 100 m²/g) exhibithigh selectivity but also exhibit activity which decreases rapidly withfalling reaction temperature.

[0105] Iron, yttrium and magnesium oxides may be utilized as primarylayers on zirconia carriers to provide both higher surface area and lowmoderator concentration.

[0106] In general, alumina has been found to be an active butunselective carrier for Pt only containing WGS catalysts. However, theselectivity of gamma alumina may be improved by doping with Y, Zr, Co,or one of the rare earth elements, such as, for example, La and Ce. Thisdoping may be accomplished by addition of the oxides or other salts suchas nitrates, in either liquid or solid form, to the alumina. Otherpossible dopants to increase the selectivity include redox dopants, suchas for instance, Re, Mo, Fe and basic dopants. Preferred is anembodiment of gamma alumina combined with yttria or with both Zr and/orCo which exhibit both high activity and selectivity over a broadtemperature range.

[0107] High surface area aluminas, such as gamma-, delta-, ortheta-alumina are preferred alumina carriers. Other alumina carriers,such as mixed silica alumina, sol-gel alumina, as well as sol-gel orco-precipitated alumina-zirconia carriers may be used. Alumina typicallyhas a higher surface area and a higher pore volume than carriers such aszirconia and offers a price advantage over other more expensivecarriers.

[0108] G. Methods of Making a WGS Catalyst

[0109] As set forth above, a WGS catalyst of the invention may beprepared by mixing the metals and/or metalloids in their elemental formsor as oxides or salts to form a catalyst precursor, which generallyundergoes a calcination and/or reductive treatment. Without being boundby theory, the catalytically active species are generally understood tobe species which are in the reduced elemental state or in other possiblehigher oxidation states.

[0110] The WGS catalysts of the invention may be prepared by any wellknown catalyst synthesis processes. See, for example, U.S. Pat. Nos.6,299,995 and 6,293,979. Spray drying, precipitation, impregnation,incipient wetness, ion exchange, fluid bed coating, physical or chemicalvapor deposition are just examples of several methods that may beutilized to make the present WGS catalysts. Preferred approaches,include, for instance, impregnation or incipient wetness. The catalystmay be in any suitable form, such as, pellets, granular, bed, ormonolith. See also the co-pending U.S. patent application Ser. No.______ filed on the same date as the present application titled “MethodsFor The Preparation Of Catalysts For Hydrogen Generation” to Hagemeyeret al. under Attorney Docket No. 7080-011-01 for further details onmethods of catalyst preparation and catalyst precursors. The completedisclosure of the above mentioned application and all other referencescited herein are incorporated herein in their entireties for allpurposes.

[0111] The WGS catalyst of the invention may be prepared on a solidsupport or carrier material. Preferably, the support or carrier is, oris coated with, a high surface area material onto which the precursorsof the catalyst are added by any of several different possibletechniques, as set forth above and as known in the art. The catalyst ofthe invention may be employed in the form of pellets, or on a support,preferably a monolith, for instance a honeycomb monolith.

[0112] Catalyst precursor solutions are preferably composed of easilydecomposable forms of the catalyst component in a sufficiently highenough concentration to permit convenient preparation. Examples ofeasily decomposable precursor forms include the nitrate, amine, andoxalate salts. Typically chlorine containing precursors are avoided toprevent chlorine poisoning of the catalyst. Solutions can be aqueous ornon-aqueous solutions. Exemplary non-aqueous solvents can include polarsolvents, aprotic solvents, alcohols, and crown ethers, for example,tetrahydrofuran and ethanol. Concentration of the precursor solutionsgenerally may be up to the solubility limitations of the preparationtechnique with consideration given to such parameters as, for example,porosity of the support, number of impregnation steps, pH of theprecursor solutions, and so forth. The appropriate catalyst componentprecursor concentration can be readily determined by one of ordinaryskill in the art of catalyst preparation.

[0113] Li—The acetate, hydroxide, nitrate and formate salts are bothpossible catalyst precursors for lithium.

[0114] Na—Sodium acetate, alkoxides including methoxide, propoxide, andethoxide, bicarbonate, carbonate, citrate, formate, hydroxide, nitrate,nitrite and oxalate may be used to prepare WGS catalysts of theinvention.

[0115] Mg—Water soluble magnesium precursors include the nitrate,acetate, lactate and formate salts.

[0116] K—Potassium nitrate, acetate, carbonate, hydroxide and formateare possible potassium catalyst precursors. The KOAc salt is volatilewith possible potassium losses when heating up to calcinationtemperature.

[0117] Ca—The nitrate, acetate and hydroxide salts, preferable saltshighly soluble in water, may be used to prepare catalysts of theinvention.

[0118] Sc—The nitrate salt, Sc(NO₃)₃ may be a precursor for scandium.

[0119] Ti—Titanium precursors which may be utilized in the presentinvention include ammonium titanyl oxalate, (NH₄)₂TiO(C₂O₄)₂, availablefrom Aldrich, and titanium(IV) bis(ammonium lactato)dihydroxide, 50 wt %solution in water, [CH₃CH(O—)CO₂NH₄]₂Ti(OH)₂, available from Aldrich.Other titanium containing precursors include Ti oxalate prepared bydissolving a Ti(IV) alkoxide, such as Ti(IV) propoxide, Ti(OCH₂CH₂CH₃)₄,(Aldrich) in 1 M aqueous oxalic acid at 60° C. and stirring for a coupleof hours, to produce a 0.72M clear colorless solution; TiO(acac)oxalateprepared by dissolving Ti(IV) oxide acetylacetonate, TiO(acac)₂,(Aldrich) in 1.5M aqueous oxalic acid at 60° C. with stirring for acouple of hours, following by cooling to room temperature overnight toproduce 1M clear yellow-brown solution; TiO(acac)₂, may also bedissolved in dilute acetic acid (50:50 HOAc:H₂O) at room temperature toproduce a 1M clear yellow solution of TiO acac. Preferably, titaniumdioxide in the anatase form is utilized as a catalyst precursormaterial.

[0120] V—Vanadium (IV) oxalate, a vanadium precursor, may be preparedfrom V₂O₅, (Aldrich), which is slurried in 1.5M aqueous oxalic acid onhot plate for 1 hour until it turns dark blue due to V(V) reduction toV(IV) by oxalic acid. Ammonium metavanadate(V), (NH₄)VO₃, (Cerac, Alfa)may be used as a precursor by dissolving it in water, preferably hot,about 80° C. water. Various polycarboxylic organic acid vanadiumprecursors can be prepared and used as catalyst precursors, for example,citric, maleic, malonic, and tatartic. Vanadium citrate can be preparedby reacting V₂O₅ with citric acid, and heating to about 80° C. Ammoniumvanadium(V) oxalate may be prepared by reacting (NH₄)VO₃ and NH₄OH inroom temperature water, increasing temperature to 90° C., stirring todissolve all solids, cooling to room temperature and adding oxalic acid;this produces a clear orange solution, which is stable for about 2 days.Ammonium vanadium(V) citrate and ammonium vanadium(V) lactate are bothprepared by shaking NH₄VO₃ in, respectively, aqueous citric acid oraqueous lactic acid, at room temperature. Diammonium vanadium(V) citratemay be prepared by dissolving, for instance, 0.25M NH₄VO₃ in citric aciddiammonium salt (Alfa) at room temperature. An exemplary method ofpreparing ammonium vanadium(V) formate is to dissolve NH₄VO₃ (0.25M) inwater at 95° C., react with 98% formic acid and NH₄OH to produce thedesired ammonium vanadium(V) formate.

[0121] Cr—Both the nitrate and acetate hydroxides are possible catalystprecursors for chromium.

[0122] Mn—Manganese nitrate, manganese acetate (Aldrich) and manganeseformate (Alfa) are all possible catalyst precursors for manganese.

[0123] Fe—Iron (III) nitrate, Fe(NO₃)₃, iron(III) ammonium oxalate,(NH₄)₃ Fe(C₂O₄)₃, iron(III) oxalate, Fe₂(C₂O₄)₃, and iron(II) acetate,Fe(OAc)₂, are all water soluble; although the iron(III)oxalate undergoesthermal decomposition at only 100° C. Potassium iron(III) oxalate,iron(III) formate and iron(III) citrate are additional iron precursors.

[0124] Co—Both cobalt nitrate and acetate are water soluble precursorsolutions. The cobalt (II) formate, Co(OOCH)₂, has low solubility incold water of about 5 g/100 ml, while cobalt (II) oxalate is soluble inaqueous NH₄OH. Another possible precursor is sodiumhexanitrocobaltate(III), Na₃Co(NO₂)₆ which is water soluble, withgradual decomposition of aqueous solutions slowed by addition of smallamounts of acetic acid. Hexaammine Co(III) nitrate is also soluble inhot (65° C.) water and NMe₄OH. Cobalt citrate, prepared by dissolvingCo(OH)₂ in aqueous citric acid at 80° C. for 1 to 2 hours, is anothersuitable cobalt precursor.

[0125] Ni—Nickel nitrate, Ni(NO₃)₂, and nickel formate are both possiblenickel precursors. The nickel formate may be prepared by dissolvingNi(HCO₂)₂ in water and adding formic acid, or by dissolving in diluteformic acid, to produce clear greenish solutions.

[0126] Cu—Copper precursors include nitrate, Cu(NO₃)₂, acetate,Cu(OAc)₂, and formate, Cu(OOCH)₂, which are increasingly less watersoluble in the order presented. Ammonium hydroxide is used to solublizeoxalate, Cu(C₂O₄)₂, and Cu(NH₃)₄(OH)₂ which is soluble in aqueous 5NNH₄OH. Copper citrate and copper amine carbonate may be prepared fromCu(OH)₂

[0127] Zn—Zinc nitrate, acetate and formate are all water soluble andpossible catalyst precursors. Ammonium zinc carbonate, (NH₄)₂Zn(OH)₂CO₃,prepared by reacting zinc hydroxide and ammonium carbonate for a week atroom temperature, is another possible precursor for zinc.

[0128] Ge—Germanium oxalate may be prepared from amorphous Ge(IV) oxide,glycol-soluble GeO₂, (Aldrich) by reaction with 1M aqueous oxalic acidat room temperature. H₂GeO₃ may be prepared by dissolving GeO₂ in waterat 80° C. and adding 3 drops of NH₄OH (25%) to produce a clear,colorless H₂GeO₃ solution. (NMe₄)₂GeO₃ may be prepared by dissolving0.25M GeO₂ in 0.1 M NMe₄OH. (NH₄)₂GeO₃ may be prepared by dissolving0.25 M GeO₂ in 0.25M NH₄OH.

[0129] Rb—The nitrate, acetate, carbonate and hydroxide salts may beused as catalyst precursors to prepare the WGS catalyst of theinvention. Preferred are water soluble salts.

[0130] Sr—The acetate is soluble in cold water to produce a clearcolorless solution.

[0131] Y—Yttrium nitrate and acetate are both possible catalystprecursors.

[0132] Zr—Zirconyl nitrate and acetate, commercially available fromAldrich, and ammonium Zr carbonate and zirconia, available from MEI, arepossible precursors for zirconium in either or both the support orcatalyst formulation itself.

[0133] Nb—Niobium oxalate prepared by dissolving niobium (V) ethoxide inaqueous oxalic acid at 60° C. for 12 hours is a possible catalystprecursor. Another preparative route to the oxalate is dissolving niobicacid or niobic oxide (Nb₂O₅) in oxalic acid at 65° C. Ammonium Nboxalate is also a possible catalyst precursor for niobium. Dissolvingniobic oxide (0.10 M Nb) in NMe₄OH (0.25 M) and stirring overnight at65° C. will produce (NMe₄)₂NbO₆.

[0134] Mo—Molybdenum containing precursor solutions may be derived fromammonium molybdate (NH₄)₂MoO₄ (Aldrich) dissolved in room temperaturewater; Mo oxalate prepared by dissolving MoO₃ (Aldrich) in 1.5M aqueousoxalic acid at 60° C. overnight; and ammonium Mo oxalate prepared from(NH₄)₆Mo₇O₂₄.4H₂O (Strem) dissolved in 1M aqueous oxalic acid at roomtemperature. (NH₄)₆Mo₇O₂₄.4H₂O (Strem) may also be dissolved in water atroom temperature to produce a stable solution of ammonium paramolybdatetetrahydrate. Molybdic acid, H₂MoO₄, (Alfa Aesar or Aldrich) may each bedissolved in room temperature water to produce 1M Mo containingsolutions.

[0135] Ru—Ru nitrosyl nitrate, Ru(NO)(NO₃)₃ (Aldrich), potassiumruthenium oxide, K₂RuO₄.H₂O, potassium perruthenate, KRuO₄, rutheniumnitrosyl acetate, Ru(NO)(OAc)₃, and tetrabutylammonium perruthenate,NBu₄RuO₄, are all possible ruthenium metal catalyst precursors.NMe₄Ru(NO)(OH)₄ solution can be prepared by dissolving Ru(NO)(OH)₃ (0.1M) (H. C. Starck) in NMe4OH (0.12M) at 80° C. produces a clear darkred-brown 0.1M Ru solution useful as a catalyst precursor solution.

[0136] Rh—A suitable rhodium catalyst precursor is Rh nitrate (Aldrichor Strem).

[0137] Pd—Catalyst compositions containing Pd can be prepared by usingprecursors like Pd nitrate, typically stabilized by dilute HNO₃, andavailable as a 10 wt. % solution from Aldrich, or Pd(NH₃)₂(NO₂)₂available as a 5 wt. % Pd commercial solution, stabilized by diluteNH₄OH. Pd(NH₃)₄(NO₃)₂ and Pd(NH₃)₄(OH)₂ are also available commercially.

[0138] Ag—Silver nitrate, silver nitrite, silver diammine nitrite, andsilver acetate are possible silver catalyst precursors.

[0139] Cd—Cadmium nitrate is water soluble and a suitable catalystprecursor.

[0140] In—Indium formate and indium nitrate are preferred precursors forindium.

[0141] Sn—Tin oxalate produced by reacting the acetate with oxalic acidmay be used as a catalyst precursor. Tin tartrate, SnC₄H₄O₆, in NMe₄OHat about 0.25 M Sn concentration, and tin acetate, also dissolved inNMe₄OH at about 0.25 M Sn concentration, may be used as catalystprecursors.

[0142] Sb—Ammonium antimony oxalate produced by reacting the acetatewith oxalic acid and ammonia is a suitable antimony precursor. Antimonyoxalate, Sb₂(C₂O₄)₃, available from Pfaltz & Bauer, is a water solubleprecursor. Potassium antimony oxide, KSbO₃, and antimony citrate,prepared by stirring antimony(II) acetate in 1 M citric acid at roomtemperature, are both possible catalyst precursors.

[0143] Te—Telluric acid, Te(OH)₆, may be used as a precursor fortellurium.

[0144] Cs—Cs salts including the nitrate, acetate, carbonate, andhydroxide are soluble in water and possible catalyst precursors.

[0145] Ba—Barium acetate and barium nitrate are both suitable precursorsfor barium catalyst components.

[0146] La—Lanthanum precursors include nitrate, La(NO₃)₃, acetate,La(OAc)₃, and perchlorate, La(ClO₄)₃, all of which may be prepared asaqueous solutions.

[0147] Ce—Ce(III) and Ce(IV) solutions may be prepared from Ce(III)nitrate hexahydrate, Ce(NO₃)₃.6H₂O, (Aldrich) and ammonium cerium(IV)nitrate, (NH₄)₂Ce(NO₃)₆, (Aldrich), respectively, by dissolution in roomtemperature water. Nitric acid, 5 vol. %, may be added to the Ce(III)salt to increase solubility and stability. Ce(OAc)₃ (Alfa) or Ce(NO₃)₄(Alfa) may also be utilized as a catalyst precursor.

[0148] Pr, Nd, Sm and Eu—The nitrate, Ln(NO₃)₃, or acetate, Ln(O₂CCH₃)₃,are possible catalyst precursors for these lanthanides.

[0149] Hf—Hafnoyl chloride and nitrate are both possible precursors.Preparing the hafnoyl nitrate by dissolving Hf(acac)₄ in dilute HNO₃ atlow heat provides a clear stable solution of hafnoyl nitrate.

[0150] Ta—Tantalum oxalate solution, Ta₂O(C₂O₄)₄, available from H. C.Starck, or prepared by dissolving Ta(OEt)₅ in aqueous oxalic acid at 60°C. for 12 hours, is a possible catalyst precursor.

[0151] W—Ammonium metatungstate hydrate, (NH₄)₆W₁₂O₃₉, is water solubleand a possible tungsten catalyst precursor. H₂WO₄ is reacted with NH₄OHand NMe₄OH, respectively, to prepare (NH₄)₂WO₄ and (NMe₄)₂WO₄ which areboth possible precursors.

[0152] Re—Rhenium oxide in H₂O₂, perrhenic acid, (HReO₄), NaReO₄ andNH₄ReO₄ are suitable rhenium precursors.

[0153] Ir—Hexachloroiridate acid, H₂IrCl₆, potassium hexacyanoiridateand potassium hexanitroiridate are all possible catalyst precursors foriridium.

[0154] Pt—Platinum containing catalyst compositions may be prepared byusing any one of a number of precursor solutions, such as,Pt(NH₃)₄(NO₃)₂ (Aldrich, Alfa, Heraeus, or Strem), Pt(NH₃)₂(NO₂)₂ innitric acid, Pt(NH₃)₄(OH)₂ (Alfa), K₂Pt(NO₂)₄, Pt(NO₃)₂, PtCl₄ andH₂PtCl₆ (chloroplatinic acid). Pt(NH₃)₄(HCO₃)₂, Pt(NH₃)₄(HPO₄),(NMe₄)₂Pt(OH)₆, H₂Pt(OH)₆, K₂Pt(OH)₆, Na₂Pt(OH)₆ and K₂Pt(CN)₆ are alsopossible choices along with Pt oxalate salts, such as K₂Pt(C₂O₄)₂. ThePt oxalate salts may be prepared from Pt(NH₃)₄(OH)₂ which is reactedwith 1M oxalic acid solution to produce a clear, colorless solution ofthe desired Pt oxalate salts.

[0155] Au—Auric acid, HAuCl₄, in dilute HCl at about 5% Au may be a goldprecursor. Gold nitrate in 0.1 M concentration may be prepared bydissolving HAu(NO₃)₄ (Alfa) in concentrated nitric acid, followed bystirring at room temperature for 1 week in the dark, then diluting 1:1with water to produce a yellow solution. It should be noted that furtherdilution may result in Au precipitation. More concentrated, 0.25M, forexample, gold nitrate may be prepared by starting with Au(OH)₃ (Alfa).NaAu(OH)₄, KAu(OH)₄, and NMe₄Au(OH)₄ may each be prepared from Au(OH)₃dissolved in bases NaOH, KOH, or NMe₄OH, respectively, in baseconcentrations ranging from, for instance, 0.25 M or higher.

[0156] 3. Producing a Hydrogen-Rich Syngas

[0157] The invention also relates to a method for producing ahydrogen-rich gas, such as a hydrogen-rich syngas. An additionalembodiment of the invention may be directed to a method of producing aCO-depleted gas, such as a CO-depleted syngas.

[0158] A CO-containing gas, such as a syngas contacts with a water gasshift catalyst in the presence of water according to the method of theinvention. The reaction preferably may occur at a temperature of lessthan 450° C. to produce a hydrogen-rich gas such as a hydrogen-richsyngas.

[0159] A method of the invention may be utilized over a broad range ofreaction conditions. Preferably, the method is conducted at a pressureof no more than about 75 bar, preferably at a pressure of no more thanabout 50 bar to produce a hydrogen-rich syngas. Even more preferred isto have the reaction occur at a pressure of no more than about 25 bar,or even no more than about 15 bar, or not more than about 10 bar.Especially preferred is to have the reaction occur at, or aboutatmospheric pressure. Depending on the formulation of the catalystaccording to the present invention, the present method may be conductedat reactant gas temperatures ranging from less than about 150° C. to upto about 450° C. Preferably, the reaction occurs at a temperatureselected from one or more temperature subranges of LTS, MTS and/or HTSas described above. Space velocities may range from about 1 hr⁻¹ up toabout 1,000,000 hr⁻¹. Feed ratios, temperature, pressure and the desiredproduct ratio are factors that would normally be considered by one ofskill in the art to determine a desired optimum space velocity for aparticular catalyst formulation.

[0160] 4. Fuel Processor Apparatus

[0161] The invention further relates to a fuel processing system forgeneration of a hydrogen-rich gas from a hydrocarbon or substitutedhydrocarbon fuel. Such a fuel processing a system would comprise, forexample, a fuel reformer, a water gas shift reactor and a temperaturecontroller.

[0162] The fuel reformer would convert a fuel reactant stream comprisinga hydrocarbon or a substituted hydrocarbon fuel to a reformed productstream comprising carbon monoxide and water. The fuel reformer maytypically have an inlet for receiving the reactant stream, a reactionchamber for converting the reactant stream to the product stream, and anoutlet for discharging the product stream.

[0163] The fuel processor system would also comprise a water gas shiftreactor for effecting a water gas shift reaction at a temperature ofless than about 450° C. This water gas shift reactor may comprise aninlet for receiving a water gas shift feed stream comprising carbonmonoxide and water from the product stream of the fuel reformer, areaction chamber having a water gas shift catalyst as described hereinlocated therein, and an outlet for discharging the resultinghydrogen-rich gas. The water gas shift catalyst would preferable beeffective for generating hydrogen and carbon dioxide from the water gasshift feed stream.

[0164] The temperature controller may be adapted to maintain thetemperature of the reaction chamber of the water gas shift reactor at atemperature of less than about 450° C.

[0165] 5. Industrial Applications

[0166] Syngas is used as a reactant feed in number of industrialapplications, including for example, methanol synthesis, ammoniasynthesis, oxoaldehyde synthesis from olefins (typically in combinationwith a subsequent hydrogenation to form the corresponding oxoalcohol),hydrogenations and carbonylations. Each of these various industrialapplications preferably includes a certain ratio of H₂ to CO in thesyngas reactant stream. For methanol synthesis the ratio of H₂:CO ispreferably about 2:1. For oxosynthesis of oxoaldehydes from olefins, theratio of H₂:CO is preferably about 1:1. For ammonia synthesis, the ratioof H₂ to N₂ (e.g., supplied from air) is preferably about 3:1. Forhydrogenations, syngas feed streams that have higher ratios of H₂:CO arepreferred (e.g., feed streams that are H₂ enriched, and that arepreferably substantially H₂ pure feed streams). Carbonylation reactionsare preferably effected using feed streams that have lower ratios ofH₂:CO (e.g., feed streams that are CO enriched, and that are preferablysubstantially CO pure feed streams).

[0167] The WGS catalysts of the present invention, and the methodsdisclosed herein that employ such WGS catalysts, can be appliedindustrially to adjust or control the relative ratio H₂:CO in a feedstream for a synthesis reaction, such as methanol synthesis, ammoniasynthesis, oxoaldehyde synthesis, hydrogenation reactions andcarbonylation reactions. In one embodiment, for example, a syngasproduct stream comprising CO and H₂ can be produced from a hydrocarbonby a reforming reaction in a reformer (e.g., by steam reforming of ahydrocarbon such as methanol or naphtha). The syngas product stream canthen be fed (directly or indirectly after further downstream processing)as the feed stream to a WGS reactor, preferably having a temperaturecontroller adapted to maintain the temperature of the WGS reactor at atemperature of about 450° C. or less during the WGS reaction (or atlower temperatures or temperature ranges as described herein inconnection with the catalysts of the present invention). The WGScatalyst(s) employed in the WGS reactor are preferably selected from oneor more of the catalysts and/or methods of the invention. The feedstream to the WGS reactor is contacted with the WGS catalyst(s) underreaction conditions effective for controlling the ratio of H₂:CO in theproduct stream from the WGS reactor (i.e., the “shifted product stream”)to the desired ratio for the downstream reaction of interest (e.g.,methanol synthesis), including to ratios described above in connectionwith the various reactions of industrial significance. As a non-limitingexample, a syngas product stream from a methane steam reformer willtypically have a H₂:CO ratio of about 6:1. The WGS catalyst(s) of thepresent invention can be employed in a WGS reaction (in the forwarddirection as shown above) to further enhance the amount of H₂ relativeto CO, for example to more than about 10:1, for a downstreamhydrogenation reaction. As another example, the ratio of H₂:CO in such asyngas product stream can be reduced by using a WGS catalyst(s) of thepresent invention in a WGS reaction (in the reverse direction as shownabove) to achieve or approach the desired 2:1 ratio for methanolsynthesis. Other examples will be known to a person of skill in the artin view of the teachings of the present invention.

[0168] A person of skill in the art will understand and appreciate thatwith respect to each of the preferred catalyst embodiments as describedin the preceding paragraphs, the particular components of eachembodiment can be present in their elemental state, or in one or moreoxide states, or mixtures thereof.

[0169] Although the foregoing description is directed to the preferredembodiments of the invention, it is noted that other variations andmodifications will be apparent to those skilled in the art, and whichmay be made without departing from the spirit or scope of the invention.

EXAMPLES

[0170] General

[0171] Small quantity catalyst composition samples are generallyprepared by automated liquid dispensing robots (Cavro ScientificInstruments) on flat quartz test wafers.

[0172] Generally, supported catalysts are prepared by providing acatalyst support (e.g. alumina, silica, titania, etc.) to the wafersubstrate, typically as a slurry composition using a liquid-handlingrobot to individual regions or locations on the substrate or bywash-coating a surface of the substrate using techniques known to thoseof skill in the art, and drying to form dried solid support material onthe substrate. Discrete regions of the support-containing substrate arethen impregnated with specified compositions intended to operate ascatalysts or catalyst precursors, with the compositions comprisingmetals (e.g. various combinations of transition metal salts). In somecircumstances the compositions are delivered to the region as a mixtureof different metal-containing components and in some circumstances(additionally or alternatively) repeated or repetitive impregnationsteps are performed using different metal-containing precursors. Thecompositions are dried to form supported catalyst precursors. Thesupported catalyst precursors are treated by calcining and/or reducingto form active supported catalytic materials at discrete regions on thewafer substrate.

[0173] The catalytic materials (e.g., supported or bulk) on thesubstrate are tested for activity and selectivity for the WGS reactionusing a scanning mass spectrometer (SMS) comprising a scanning/sniffingprobe and a mass spectrometer. More details on the scanning massspectrometer instrument and screening procedure are set forth in U.S.Pat. No. 6,248,540, in European Patent No. EP 1019947 and in EuropeanPatent Application No. EP 1186892 and corresponding U.S. applicationSer. No. 09/652,489 filed Aug. 31, 2000 by Wang et al., the completedisclosure of each of which is incorporated herein in its entirety.Generally, the reaction conditions (e.g. contact time and/or spacevelocities, temperature, pressure, etc.) associated with the scanningmass spectrometer catalyst screening reactor are controlled such thatpartial conversions (i.e., non-equilibrium conversions, e.g., rangingfrom about 10% to about 40% conversion) are obtained in the scanningmass spectrometer, for discrimination and ranking of catalyst activitiesfor the various catalytic materials being screened. Additionally, thereaction conditions and catalyst loadings are established such that theresults scale appropriately with the reaction conditions and catalystloadings of larger scale laboratory research reactors for WGS reactions.A limited set of tie-point experiments are performed to demonstrate thescalability of results determined using the scanning mass spectrometerto those using larger scale laboratory research reactors for WGSreactions. See, for example, Example 12 of U.S. Provisional PatentApplication Serial No. 60/434,708 entitled “Platinum-RutheniumContaining Catalyst Formulations for Hydrogen Generation” filed byHagemeyer et al. on Dec. 20, 2002.

[0174] Preparative and Testing Procedures

[0175] The catalysts and compositions of the present invention wereidentified using high-throughput experimental technology, with thecatalysts being prepared and tested in library format, as describedgenerally above, and in more detail below. Specifically, such techniqueswere used for identifying catalyst compositions that were active andselective as WGS catalysts. As used in these examples, a “catalystlibrary” refers to an associated collection of candidate WGS catalystsarrayed on a wafer substrate, and having at least two, and typicallythree or more common metal components (including metals in the fullyreduced state, or in a partially or fully oxidized state, such as metalsalts), but differing from each other with respect to relativestoichiometry of the common metal components.

[0176] Depending on the library design and the scope of theinvestigation with respect to a particular library, multiple (i.e., twoor more) libraries were typically formed on each wafer substrate. Afirst group of test wafers each comprised about 100 different catalystcompositions formed on a three-inch wafer substrate, typically with mostcatalysts being formed using at least three different metals. A secondgroup of test wafers each comprised about 225 different catalystcompositions on a four-inch wafer substrate, again typically with mostcatalysts being formed using at least three different metals. Each testwafer itself typically comprised multiple libraries. Each librarytypically comprised binary, ternary or higher-order compositions—thatis, for example, as ternary compositions that comprised at least threecomponents (e.g., A, B, C) combined in various relative ratios to formcatalytic materials having a molar stoichiometry covering a range ofinterest (e.g., typically ranging from about 20% to about 80% or more(e.g. to about 100% in some cases) of each component). For supportedcatalysts, in addition to varying component stoichiometry for theternary compositions, relative total metal loadings were alsoinvestigated.

[0177] Typical libraries formed on the first group of (three-inch) testwafers included, for example, “five-point libraries” (e.g., twentylibraries, each having five different associated catalyst compositions),or “ten-point” libraries (e.g., ten libraries, each having ten differentassociated catalyst compositions), or “fifteen-point libraries” (e.g.,six libraries, each having fifteen different associated catalystcompositions) or “twenty-point libraries” (e.g., five libraries, eachhaving twenty different associated catalyst compositions). Typicallibraries formed on the second group of (four-inch) test wafersincluded, for example, “nine-point libraries” (e.g., twenty-fivelibraries, each having nine different associated catalyst compositions),or “twenty-five point” libraries (e.g., nine libraries, each havingtwenty-five different associated catalyst compositions). Largercompositional investigations, including “fifty-point libraries” (e.g.,two or more libraries on a test wafer, each having fifty associatedcatalyst compositions), were also investigated. Typically, thestoichiometric increments of candidate catalyst library members rangedfrom about 1.5% (e.g. for a “fifty-five point ternary”) to about 15%(e.g., for a “five-point” ternary). See, generally, for example, WO00/17413 for a more detailed discussion of library design and arrayorganization. FIGS. 8A-8F of the instant application shows librarydesigns for libraries prepared on a common test wafer, as graphicallyrepresented using Library Studios® (Symyx Technologies, Inc., SantaClara, Calif.), where the libraries vary with respect to bothstoichiometry and catalyst loading. Libraries of catalytic materialsthat vary with respect to relative stoichiometry and/or relativecatalyst loading can also be represented in a compositional table, suchas is shown in the several examples of this application.

[0178] Referring to FIG. 8A, for example, the test wafer includes ninelibraries, where each of the nine libraries comprise nine differentternary compositions of the same three-component system. In thenomenclature of the following examples, such a test wafer is said toinclude nine, nine-point-ternary (“9PT”) libraries. The library depictedin the upper right hand corner of this test wafer includes catalystcompositions comprising components A, B and X₁ in 9 differentstoichiometries. As another example, with reference to FIG. 8B, apartial test wafer is depicted that includes a fifteen-point-ternary(“15PT”) library having catalyst compositions of Pt, Pd and Cu infifteen various stoichiometries. Generally, the composition of eachcatalyst included within a library is graphically represented by anassociation between the relative amount (e.g., moles or weight) ofindividual components of the composition and the relative area shown ascorresponding to that component. Hence, referring again to the fifteendifferent catalyst compositions depicted on the partial test waferrepresented in FIG. 8B, it can be seen that each composition includes Pt(dark grey), Pd (light grey) and Cu (black), with the relative amount ofPt increasing from column 1 to column 5 (but being the same as comparedbetween rows within a given column), with the relative amount of Pddecreasing from row 1 to row 5 (but being the same as compared betweencolumns within a given row), and with the relative amount of Cudecreasing from a maximum value at row 5, column 1 to a minimum at, forexample, row 1, column 1. FIG. 8C shows a test wafer that includes afifty-point-ternary (“50PT”) library having catalyst compositions of Pt,Pd and Cu in fifty various stoichiometries. This test library could alsoinclude another fifty-point ternary library (not shown), for examplewith three different components of interest.

[0179]FIGS. 8D-8F are graphical representations of two fifty-pointternary libraries (“bis 50PT libraries”) at various stages ofpreparation—including a Pt—Au—Ag/CeO₂ library (shown as the upper rightternary library of FIG. 8E) and a Pt—Au—Ce/ZrO₂ library (shown as thelower left ternary library of FIG. 8E). Note that the Pt—Au—Ag/CeO₂library also includes binary-impregnated compositions—Pt—Au/CeO₂ binarycatalysts (row 2) and Pt—Ag/CeO₂ (column 10). Likewise, thePt—Au—Ce/ZrO₂ library includes binary-impregnatedcompositions—Pt—Ce/ZrO₂ (row 11) and Au—Ce/ZrO₂ (column 1). Briefly, thebis 50PT libraries were prepared by depositing CeO₂ and ZrO₂ supportsonto respective portions of the test wafer as represented graphically inFIG. 8D. The supports were deposited onto the test wafer as a slurry ina liquid media using a liquid handling robot, and the test wafer wassubsequently dried to form dried supports. Thereafter, salts of Pt, Auand Ag were impregnated onto the regions of the test wafer containingthe CeO₂ supports in the various relative stoichiometries as representedin FIG. 8E (upper-right-hand library). Likewise, salts of Pt, Au and Cewere impregnated onto the regions of the test wafer containing the ZrO₂supports in the various relative stoichiometries as represented in FIG.8E (lower-left-hand library). FIG. 8F is a graphical representation ofthe composite library design, including the relative amount of catalystsupport.

[0180] Specific compositions of tested catalytic materials of theinvention are detailed in the following examples for selected libraries.

[0181] Performance benchmarks and reference experiments (e.g., blanks)were also provided on each quartz catalyst test wafer as a basis forcomparing the catalyst compositions of the libraries on the test wafer.The benchmark catalytic material formulations included a Pt/zirconiacatalyst standard with about 3% Pt catalyst loading (by weight, relativeto total weight of catalyst and support). The Pt/zirconia standard wastypically synthesized by impregnating 3 μL of, for example, 1.0% or 2.5%by weight, Pt stock solution onto zirconia supports on the wafer priorto calcination and reduction pretreatment.

[0182] Typically wafers were calcined in air at a temperature rangingfrom 300° C. to 500° C. and/or reduced under a continuous flow of 5%hydrogen at a temperature ranging from about 200° C. to about 500° C.(e.g., 450° C.). Specific treatment protocols are described below withrespect to each of the libraries of the examples.

[0183] For testing using the scanning mass spectrometer, the catalystwafers were mounted on a wafer holder which provided movement in an XYplane. The sniffing/scanning probe of the scanning mass spectrometermoved in the Z direction (a direction normal to the XY plane of movementfor the wafer holder), and approached in close proximity to the wafer tosurround each independent catalyst element, deliver the feed gas andtransmit the product gas stream from the catalyst surface to thequadrupole mass spectrometer. Each element was heated locally from thebackside using a CO₂ laser, allowing for an accessible temperature rangeof about 200° to about 600° C. The mass spectrometer monitored sevenmasses for hydrogen, methane, water, carbon monoxide, argon, carbondioxide and krypton: 2, 16, 18, 28, 40, 44 and 84, respectively.

[0184] Catalyst compositions were tested at various reactiontemperatures, typically including for example at about 250° C., 300° C.,350° C. and/or 400° C. Particularly for LTS formulations, testing ofcatalyst activity at reaction temperatures may start as low as 200° C.The feed gas typically consisted of 51.6% H₂, 7.4% Kr, 7.4% CO, 7.4% CO₂and 26.2% H₂O. The H₂, CO, CO₂ and Kr internal standard are premixed ina single gas cylinder and then combined with the water feed. Treatedwater (18.1 mega-ohms-cm at 27.5° C.) produced by a Barnstead Nano PureUltra Water system was used, without degassing.

[0185] Data Processing and Analysis

[0186] Data analysis was based on mass balance plots where CO conversionwas plotted versus CO₂ production. The mass spectrometer signals wereuncalibrated for CO and CO₂ but were based on Kr-normalized massspectrometer signals. The software package SpotFire™ (sold by SpotFire,Inc. of Somerville, Mass.) was used for data visualization.

[0187] A representative plot of CO conversion versus CO₂ production fora WGS reaction is shown in FIG. 9A involving, for discussion purposes,two ternary catalyst systems—a Pt—Au—Ag/CeO₂ catalyst library and aPt—Au—Ce/ZrO₂ catalyst library—as described above in connection withFIGS. 8D-8F. The catalyst compositions of these libraries were screenedat four temperatures: 250° C., 300° C., 350° C. and 400° C. Withreference to the schematic diagram shown in FIG. 10B, active and highlyselective WGS catalysts (e.g., Line I of FIG. 9B) will approach a linedefined by the mass balance for the water-gas-shift reaction (the “WGSdiagonal”) with minimal deviation, even at relatively high conversions(i.e., at CO conversions approaching the thermodynamic equilibriumconversion (point “TE” on FIG. 9B)). Highly active catalysts may beginto deviate from the WGS diagonal due to cross-over to the competingmethanation reaction (point “M” on FIG. 9C). Catalyst compositions thatexhibit such deviation may still, however, be useful WGS catalystsdepending on the conversion level at which such deviation occurs. Forexample, catalysts that first deviate from the WGS diagonal at higherconversion levels (e.g., Line II of FIG. 9B) can be employed aseffective WGS catalysts by reducing the overall conversion (e.g., bylowering catalyst loading or by increasing space velocity) to theoperational point near the WGS diagonal. In contrast, catalysts thatdeviate from the WGS diagonal at low conversion levels (e.g., Line IIIof FIG. 9B) will be relatively less effective as WGS catalysts, sincethey are unselective for the WGS reaction even at low conversions.Temperature affects the thermodynamic maximum CO conversion, and canaffect the point of deviation from the mass-balance WGS diagonal as wellas the overall shape of the deviating trajectory, since lowertemperatures will generally reduce catalytic activity. For somecompositions, lower temperatures will result in a more selectivecatalyst, demonstrated by a WGS trajectory that more closelyapproximates the WGS mass-balance diagonal. (See FIG. 9C). Referringagain to FIG. 9A, it can be seen that the Pt—Au—Ag/CeO₂ and thePt—Au—Ce/ZrO₂ catalyst compositions are active and selective WGScatalysts at each of the screened temperatures, and particularly atlower temperatures.

[0188] Generally, the compositions on a given wafer substrate weretested together in a common experimental run using the scanning massspectrometer and the results were considered together. In thisapplication, candidate catalyst compositions of a particular library onthe substrate (e.g., ternary or higher-order catalysts comprising threeor more metal components) were considered as promising candidates for anactive and selective commercial catalyst for the WGS reaction based on acomparison to the Pt/ZrO₂ standard composition included on that wafer.Specifically, libraries of catalytic materials were deemed to beparticularly preferred WGS catalysts if the results demonstrated that ameaningful number of catalyst compositions in that library comparedfavorably to the Pt/ZrO₂ standard composition included on the wafersubstrate with respect to catalytic performance. In this context, ameaningful number of compositions was generally considered to be atleast three of the tested compositions of a given library. Also in thiscontext, favorable comparison means that the compositions had catalyticperformance that was as good as or better than the standard on thatwafer, considering factors such as conversion, selectivity and catalystloading. All catalyst compositions of a given library were in many casespositively identified as active and selective WGS catalysts even insituations where only some of the library members compared favorably tothe Pt/ZrO₂ standard, and other compositions within that librarycompared less than favorably to the Pt/ZrO₂ standard. In suchsituations, the basis for also including members of the library thatcompared somewhat less favorably to the standard is that these membersin fact positively catalyzed the WGS reaction (i.e., were effective ascatalysts for this reaction). Additionally, it is noted that suchcompositions may be synthesized and/or tested under more optimally tunedconditions (e.g., synthesis conditions, treatment conditions and/ortesting conditions (e.g., temperature)) than occurred during actualtesting in the library format, and significantly, that the optimalconditions for the particular catalytic materials being tested maydiffer from the optimal conditions for the Pt/ZrO₂ standard—such thatthe actual test conditions may have been closer to the optimalconditions for the standard than for some of the particular members.Therefore, it was specifically contemplated that optimization ofsynthesis, treatment and/or screening conditions, within the generallydefined ranges of the invention as set forth herein, would result ineven more active and selective WGS catalysts than what was demonstratedin the experiments supporting this invention. Hence, in view of theforegoing discussion, the entire range of compositions defined by eachof the claimed compositions (e.g., each three-component catalyticmaterial, or each four-component catalytic material) was demonstrated asbeing effective for catalyzing the WGS reaction. Further optimization isconsidered, with various specific advantages associated with variousspecific catalyst compositions, depending on the desired or requiredcommercial application of interest. Such optimization can be achieved,for example, using techniques and instruments such as those described inU.S. Pat. No. 6,149,882, or those described in WO 01/66245 and itscorresponding U.S. applications, U.S. Ser. No. 09/801,390, entitled“Parallel Flow Process Optimization Reactor” filed Mar. 7, 2001 by Berghet al., and U.S. Ser. No. 09/801,389, entitled “Parallel Flow ReactorHaving Variable Feed Composition” filed Mar. 7, 2001 by Bergh et al.,each of which are incorporated herein by reference for all purposes.

[0189] Additionally, based on the results of screening of initiallibraries, selective additional “focus” libraries were selectivelyprepared and tested to confirm the results of the initial libraryscreening, and to further identify better performing compositions, insome cases under the same and/or different conditions. The test wafersfor the focus libraries typically comprised about 225 differentcandidate catalyst compositions formed on a four-inch wafer substrate,with one or more libraries (e.g. associated ternary compositions A, B,C) formed on each test wafer. Again, the metal-containing components ofa given library were typically combined in various relative ratios toform catalysts having stoichiometry ranging from about 0% to about 100%of each component, and for example, having stoichiometric increments ofabout 10% or less, typically about 2% or less (e.g., for a “fifty-sixpoint ternary”). Focus libraries are more generally discussed, forexample, in WO 00/17413. Such focus libraries were evaluated accordingto the protocols described above for the initial libraries.

[0190] The raw residual gas analyzer (“rga”) signal values generated bythe mass spectrometer for the individual gases are uncalibrated andtherefore different gases may not be directly compared. Methane data(mass 16) was also collected as a control. The signals are typicallystandardized by using the raw rga signal for krypton (mass 84) to removethe effect of gas flow rate variations. Thus, for each library element,the standardized signal is determined as, for example, sH₂O=raw H₂O/rawKr; sCO=raw CO/raw Kr; sCO₂=raw CO₂/raw Kr and so forth.

[0191] Blank or inlet concentrations are determined from the average ofthe standardized signals for all blank library elements, i.e. libraryelements for which the composition contains at most only support. Forexample, b_(avg) H₂O=average sH₂O for all blank elements in the library;b_(avg) CO=average sCO for all blank elements in the library; and soforth.

[0192] Conversion percentages are calculated using the blank averages toestimate the input level (e.g., b_(avg) CO) and the standardized signal(e.g., sCO) as the output for each library element of interest. Thus,for each library element, CO_(conversion)=100×(b_(avg) CO−sCO)/b_(avg)CO and H₂O_(conversion)=100×(b_(avg) H₂O−sH₂O)/b_(avg) H₂O.

[0193] The carbon monoxide (CO) to carbon dioxide (CO₂) selectivity isestimated by dividing the amount of CO₂ produced (sCO₂−b_(avg) CO₂) bythe amount of CO consumed (b_(avg) CO−sCO). The CO₂ and CO signals arenot directly comparable because the rga signals are uncalibrated.However, an empirical conversion constant (0.6 CO₂ units=1 CO unit) hasbeen derived, based on the behavior of highly selective standardcatalyst compositions. The selectivity of the highly selective standardcatalyst compositions approach 100% selectivity at low conversion rates.Therefore, for each library element, estimated CO to CO₂selectivity=100×0.6×(sCO₂−b_(avg) CO₂)/(b_(avg) CO−sCO). Low COconsumption rates can produce highly variable results, and thus thereproducibility of CO₂ selectivity values is maintained by artificiallylimiting the CO₂ selectivity to a range of 0 to 140%.

[0194] The following examples are representative of the screening oflibraries that lead to identification of the particularly claimedinventions herein.

Example 1

[0195] A 4′ quartz wafer with 256 wells was precoated with zirconiacarrier by repeated slurry dispensing zirconia (ZrO₂ Norton XZ16052/MEIFZ0923 70:30 mixture, 2×4 μl=8 μl zirconia slurry, 1 g ZrO₂ mix slurriedin 4 ml EG/H₂O 1:1) onto the wafer.

[0196] The zirconia carrier-precoated wafer was dried and thenimpregnated with Pt by Cavro dispensing from a Pt(NH₃)₂(NO₂)₂ stocksolution (5 wt. % Pt) to a microtiter plate (5-point (“5P”) Pt gradient)followed by transferring replicas (i.e., repeated daughtering) of the 5PPt gradient onto the wafer (3 μl dispense volume per well, 45replicas=45 identical 5-point Pt gradients on the wafer).

[0197] The wafer was dried and then impregnated with Rh by Cavrodispensing from a Rh nitrate stock solution vial (1% Rh) to a microtiterplate (5-point Rh gradient) followed by transferring replicas of the 5PRh gradient onto the wafer (3 μl dispense volume per well, 45replicas=45 identical 5-point Rh gradients on the wafer).

[0198] The wafer was dried and then impregnated with nine differentmetals by Cavro dispensing from metal precursor stock solutions (Ag, Cunitrate; Sn, Sb, Ge oxalate; Fe, Ce, Co nitrate; Ti oxalate) to amicrotiter plate (5-point metal gradients) followed by transferringreplicas of the 5P metal gradients onto the wafer (3 μl dispense volumeper well, 5 replicas per metal=5 identical 5-point metal gradients onthe wafer for each of the 9 metals).

[0199] Thus, the nine 25-point ternaries Pt—Rh—{Ag, Cu, Sn, Sb, Ge, Fe,Ce, Co, Ti} are mapped out as 5 by 5 squares with orthogonal gradients.Six internal Pt/ZrO₂ standards were spotted in the first row and lastcolumn (4 μl ZrO₂ slurry/dry/3 μl Pt(NH₃)₂(NO₂)₂ (2.5% Pt). Commercialcatalyst was slurried into five positions of the first row and lastcolumn as external standards (3 μl catalyst slurry). See FIGS. 1A-1D.

[0200] The wafer was dried, calcined in air at 450° C. for 2 hours andthen reduced in 5% H₂/Ar at 450° C. for 2 hours. The reduced library wasthen screened by SMS for WGS activity with a H₂/CO/CO₂/H₂O mixed feed at250° C., 300° C., 350° C. and 400° C. Results at 250° C., 300° C., 350°C. and 400° C. are presented in FIGS. 1E-1I.

[0201] It was found that Rh can efficiently be moderated by Pt and thatPt—Rh forms a synergistic pair. It was realized that theactivity/selectivity of Pt—Rh combination can be fine-tuned by selectionof dopants among the synergistic moderators Ce, Ti, Ag, Sb, Ge and Fe.Pt—Rh—{Ce,Ti} were found to be the most active and promising for highflow HTS application. Pt—Rh—{Ag,Au,Sb,Ge,Fe} were found to be moreselective and therefore promising for MTS and/or HTS applications.

Example 2

[0202] A 4′ quartz wafer with 256 wells was precoated with zirconiacarrier by repeated slurry dispensing zirconia (ZrO₂ Norton XZ16052/MEIFZO923 70:30 mixture, 2×4 μl=8 μl zirconia slurry, 1 g ZrO₂ mix slurriedin 4 ml EG/H₂O 1:1) onto the wafer.

[0203] The zirconia carrier-precoated wafer was dried and thenimpregnated with Pt by Cavro dispensing from a Pt(NH₃)₂(NO₂)₂ stocksolution (2.5% Pt) directly onto the wafer 3 μl dispense volume/well).Six internal standards were spotted into 6 first row/last column wells(4 μl zirconia slurry+3 μl 2.5% Pt solution).

[0204] The wafer was dried and then impregnated with CoRu and RuPtgradients by Cavro dispensing from Co nitrate (0.5M Co), Ru nitrosylnitrate (1% Ru) and Pt(NH₃)₂(NO₂)₂ (5% Pt) stock solution vials to amicrotiter plate followed by transferring replicas of the 8-point and7-point gradients onto the wafer (3 μl dispense volume/well). The waferwas dried and then impregnated with FeCo by Cavro dispensing from Fenitrate (1M Fe) and Co nitrate (0.5M Co) stock solution vials to amicrotiter plate (8-point and 7-point gradients) followed bytransferring replicas of the Fe—H₂O and Fe—Co gradients onto the wafer(3 μl dispense volume per well). The wafer was dried and thenimpregnated with Pt by Cavro dispensing from a Pt(NH₃)₂(NO₂)₂ stocksolution (2.5% Pt) directly onto the wafer 3 μl dispense volume/well).

[0205] Thus four sub-libraries: 8×8 quaternary Pt—Ru—Co—Fe (Pt first)and 8×7 quaternary Pt—Ru—Co—Fe (Pt last, to check the effect of order ofPt addition) and 7×8 ternary Ru—Co—Fe and 7×7 quaternary Pt—Ru—Co—Fe aremapped out as rectangles/squares with orthogonal gradients. The waferwas dried, calcined in air at 500° C. for 1 hour and then reduced in 5%H₂/Ar at 400° C. for 3 hours. Commercial catalyst was slurried into fivepositions of the first row and last column as external standards (3 μlcatalyst slurry). See FIGS. 2A-2G.

[0206] The reduced library was then screened in SMSII for WGS activitywith a H₂/CO/CO₂/H₂O mixed feed at 250° C., 300° C., 350° C. and 400° C.This set of experiments demonstrated active and selective WGS catalystformulations of various {Pt, blank}-{Ru—Co—Fe}/ZrO₂ formulations, withPt present as either a first or last layer on the wafer.

Example 3

[0207] A 4″ quartz wafer was precoated with Norton XZ 16052 ZrO₂, NortonXT TiO₂ and Aldrich CeO₂ by slurry dispensing 1×6 μL slurry, (700 mgXZ16052 and 300 mg FZO ZrO₂ slurried in 4 mL EG/H₂O 5:5; 500 mg TiO₂slurried in 4 mL EG/H₂O 5:5; 1 g CeO₂ slurried in 3 mL EG/H₂O 5:5) ontothe wafer. The precoated wafer has dried and then six internal standardswere spotted into six first row/last column wells (4 μL zirconiaslurry+3 μL 2.5% Pt(NH₃)₂(NO₂)₂ solution). The wafer was dried and thenimpregnated by Cavro dispensing with gradients of Co nitrate (1M Co), Tioxalate (1M Ti), Mo oxalate (1M Mo) from stock solutions to a microtiterplate followed by transferring 15 replicas onto the wafer (3 μL dispensevolume/well).

[0208] The wafer was dried and then impregnated by Cavro dispensing withRu nitrosylnitrate (1.5% Ru) and Pt(NH₃)₂(NO₂)₂ (5% Pt) from stocksolution vials to a microtiter plate followed by transferring replicasonto the wafer (3 μL dispense volume/well). Commercial catalyst wasslurried into five positions of the first row and last column asexternal standards (3 μl catalyst slurry). See FIGS. 3A-3F.

[0209] The wafer was dried, calcined at 450° C. in air and then reducedin 5% H₂/Ar at 450° C. for 2 hours. The reduced library was thenscreened by SMS for WGS activity with a H₂/CO/CO₂/H₂O mixed feed at 250°C., 300° C., 350° C. and 400° C. This set of experiments demonstratedactive and selective WGS catalyst formulations of various {Co, Ti,Mo}—{Pt—Ru}/{ZrO₂, TiO₂, CeO₂} formulations on the wafer.

Example 4

[0210] A 3′ quartz wafer was coated with niobia, ceria and magnesiacarriers by slurry-dispensing aqueous carrier slurries onto the wafer (4μl slurry/well, 1 g of carrier powder slurried in 2 ml H₂O for niobiaand ceria; 500 mg of carrier powder slurried in 2 ml H₂O for magnesia).Niobia carriers were produced by Norton, product numbers 2001250214,2000250356, 2000250355, 2000250354 and 2000250351. Cerias came fromNorton (product numbers 2001080053, 2001080052 and 2001080051) andAldrich (product number 21,157-50. Magnesia was obtained from Aldrich(product number 24,338-8).

[0211] The carrier precoated wafer was then loaded with the same Ptgradient for each carrier in a single impregnation step by liquiddispensing 3 μl Pt(NH₃)₂(NO₂)₂ solution (5% Pt) from microtiter plate towafer. The wafer was dried and then reduced in 5% H₂/Ar at 450° C. for 2hours. See FIGS. 4A-4C.

[0212] The reduced library was then screened in SMS for WGS activitywith a H₂/CO/CO₂/H₂O mixed feed at 250° C., 300° C., 350° C. and 400° C.Results at 250° C., 300° C., 350° C. and 400° C. are presented in FIGS.4D-4H.

[0213] This set of experiments demonstrated active and selective WGScatalyst formulations of various Pt on one of Nb oxide, Ce oxide or Mgoxide formulations on the wafer. Various Norton niobia carriers werefound to be very active and selective over a broad temperature range.Norton ceria 2001080051 was found to be very selective at highertemperatures. Magnesia was less active than either of niobia or ceriabut did exhibit highly selective WGS performance.

Example 5

[0214] A 4′ quartz wafer was precoated with zirconia carrier by repeatedslurry dispensing zirconia powder (Norton Xz16052) onto the wafer. Theslurry was composed of 1.5 g zirconia powder in 4 mL of a MEO/EG/H₂O40:30:30 mixture. A total of 3 μL of slurry was deposited on each spot.

[0215] The zirconia carrier precoated wafer was impregnated with a 7point concentration gradient of Ti, Zr, V, Mo and Co and an 8 pointconcentration gradient of Ge, Sn, Sb, La and Ce by Cavro dispensing frommetal stock solution vials to a microtiter plate (single column 7-point(“7P”) and 8-point (“8P”) concentration gradients, respectively followedby transferring replicas of the four 7P and 8P columns onto the wafer(2.5 μl dispense volume per well). La, Ce, Zr and Co were provided astheir nitrates, Ti as the ammonium titanyl oxalate, Sb as the ammoniumantimony oxalate, Mo as molybdic acid and V, Ge and Sn as the oxalates.

[0216] The wafer was dried at 70° C. for 10 minutes and then impregnatedwith Fe, Ru and Rh concentration gradients by Cavro dispensing from Fenitrate (0.5 M Fe), Ru nitrosyl nitrate (0.5% Ru) and Rh nitrate (0.5%Rh) stock solution vials to a microtiter plate (single row 7-point and8-point gradients) followed by transferring replicas of the three 7P and8P rows onto the wafer (2.5 μl dispense volume per well). The wafer wasdried at 70° C. for 10 minutes and was then uniformly coated with 2.5μl/well of a Pt(NH₃)₂(NO₂)₂ stock solution (1% Pt). The wafer wascalcined in air at 450° C. for 2 hours followed by reduction with 5%H₂/N₂ at 450° C. for 2 hours. Six internal standards were synthesized byspotting 3 μl Pt(NH₃)₂(NO₂)₂ solution (1.0% Pt) into the correspondingfirst row/last column positions. See FIG. 5A-5I.

[0217] The reduced library was then screened in SMS for WGS activitywith a H₂/CO/CO₂/H₂O mixed feed at 300° C. and 350° C. The CO conversionversus CO₂ production results at 300° C. and 350° C. are presented inFIGS. 5J, 5K, and 5L. More detailed test results, such as, COconversion, CO₂ production and CH₄ production at 300° C. and 350° C. foreach of the 225 individual catalyst wells on the test wafer arepresented in Table 1.

[0218] This set of experiments demonstrated active and selective WGScatalyst formulations of various Pt—[Fe, Ru, Rh}—{Ti, Zr, V, Mo, Co, Ge,Sn, Sb, La, Ce}/ZrO₂ formulations on the wafer.

Example 6

[0219] A 4′ quartz wafer was coated with fourteen different catalystcarriers by slurry-dispensing the carrier slurries onto the wafer. Eachwafer column was coated with a different carrier, except for columns 14and 15 which were both coated with gamma-alumina, described below:

[0220] 1) Ceria, 99.5% purity; 9 to 15 nm particle size; BET (m²/g):55-95; Alfa 43136; dispensed onto the wafer from a slurry of 0.75 gpowder slurried in 4 mL ethylene glycol (“EG”)/H₂O/MEO 40:30:30 mixture.

[0221] 2) Ceria, produced by the low temperature calcination ofprecipitated Ce hydroxide; dispensed onto the wafer from a slurry of 1.5g powder slurried in 4 mL EG/H₂O/MEO 40:30:30 mixture.

[0222] 3) Zirconia; 99.8% purity; BET (m²/g): greater than 90; NortonXZ16052; dispensed onto the wafer from a slurry of 1.5 g powder slurriedin 4 mL EG/H₂O/MEO 40:30:30 mixture.

[0223] 4) Zirconia; 99.8% purity; BET (m²/g): 269; Norton XZ16154;dispensed onto the wafer from a slurry of 1.5 g powder slurried in 4 mLEG/H₂O/MEO 40:30:30 mixture.

[0224] 5) Titania; BET (m²/g): 45; Degussa Aerolyst 7708; dispensed ontothe wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H₂O/MEO40:30:30 mixture.

[0225] 6) Titania; 99% purity; BET (m²/g): 37; Norton XT25384; dispensedonto the wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H₂O/MEO40:30:30 mixture.

[0226] 7) Niobia; 97% purity; BET (m²/g): 27; Norton 355; dispensed ontothe wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H₂O/MEO40:30:30 mixture.

[0227] 8) Lanthania; 99.999% purity; Gemre-5N from Gemch Co., Ltd.(Shanghai, China); dispensed onto the wafer from a slurry of 1.5 gpowder slurried in 4 mL EG/H₂O/MEO 40:30:30 mixture.

[0228] 9) Mixed Fe—Ce—O; coprecipitated Fe and Ce oxalate; calcined at360° C.; dispensed onto the wafer from a slurry of 1.0 g powder slurriedin 4 mL EG/H₂O/MEO 40:30:30 mixture.

[0229] 10) Mixed La—Ce—O; coprecipitated La and Ce oxalate; calcined at760° C.; dispensed onto the wafer from a slurry of 1.0 g powder slurriedin 4 mL EG/H₂O/MEO 40:30:30 mixture.

[0230] 11) Mixed Sb₃O₄—SnO₂ carrier from Alfa; 99.5% purity; BET (m²/g):30-80; Sb₃O₄:SnO₂ ratio is 10:90 by weight; dispensed onto the waferfrom a slurry of 1.0 g powder slurried in 4 mL EG/H₂O/MEO 40:30:30mixture.

[0231] 12) Mixed Fe—Cr—Al—O; commercially available high temperaturewater gas shift catalyst; dispensed onto the wafer from a slurry of 1.0powder slurried in 4 mL EG/H₂O/MEO 40:30:30 mixture.

[0232] 13) Fe₂O₃/FeOOH; BET (m²/g): 14; 50:50 physical mixture ofcommercial powders (Bayferrox 720N: Bayoxide E3920 from Bayer);dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mLEG/H₂O/MEO 40:30:30 mixture.

[0233] 14 and 15) Gamma-Al₂O₃; BET (m²/g): 150; Condea Catalox Sba150;dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mLEG/H₂O/MEO 40:30:30 mixture.

[0234] In all cases, except for carrier 1, the slurries were applied in3 μL per well; carrier 1 was deposited as two aliquots of 3 μl/well. Thewafer was then dried at 70° C. for 10 minutes.

[0235] Columns 14 and 15 were coated with 2.5 μL per well of zirconylnitrate (0.25M) and lanthanum nitrate (0.25M), respectively, then driedfor 10 minutes at 70° C. The first 13 columns of the carrier coatedwafer were then loaded with a 15 point Pt gradient by liquid dispensingof 3 μL Pt(NH₃)₂(NO₂)₂ solution (1% Pt) from microtiter plate to wafer.The wafer was dried at 70° C. for 10 minutes. Columns 14 and 15 werethen loaded with a 15 point Pt gradient by liquid dispensing of 3 μLPt(NH₃)₂(NO₂)₂ solution (1% Pt) from microtiter plate to wafer. Thewafer was dried at 70° C. for 10 minutes, calcined in air at 350° C. for2 hours, then reduced in 5% H₂/Ar at 450° C. for 2 hours. Six internalstandards were synthesized by spotting 3 μL Pt(NH₃)₂(NO₂)₂ solution(1.0% Pt) into the corresponding first row/last column positions. SeeFIGS. 6A-5F.

[0236] The reduced library was then screened in SMS for WGS activitywith a H₂/CO/CO₂/H₂O mixed feed at 250° C. and 300° C. The CO conversionversus CO₂ production results at 250° C. and 300° C. are presented inFIGS. 6G, 6H, and 6I. More detailed test results, such as, COconversion, CO₂ production and CH₄ production at 250° C. and 300° C. foreach of the 225 individual catalyst wells on the test wafer arepresented in Table 2.

[0237] This set of experiments demonstrated active and selective WGScatalyst formulations of various Pt on various of the oxide carrierformulations on the wafer.

Example 7

[0238] Scale-up catalyst samples were prepared by using incipientwetness impregnation of 0.75 grams of ZrO₂ support (Norton, 80-120 mesh)which had been weighed into a 10-dram vial. Aqueous metal precursor saltsolutions were then added in the order: Rh, Co, Fe, Mo, V, Pt, andfinally K. The precursor salt solutions were tetraammineplatinum (II)hydroxide solution (9.09% Pt (w/w)), rhodium (III) nitrate (1.0% Rh(w/w)), cobalt (II) nitrate (1.0M), molydbic acid (1.0M), vanadiumcitrate (1.0M), iron (III) nitrate (1.0M), and potassium hydroxide(13.92% K (w/w)). All reagents were nominally research grade fromAldrich, Strem, or Alfa. Following each metal addition, the catalystswere dried at 80° C. overnight and then calcined in air as follows:After Pt addition 300 ° C. for 3 hours After Rh, Co, or Fe addition 450° C. for 3 hours After Mo or V addition 350 ° C. for 3 hours.

[0239] Following K addition, the catalysts were calcined at 300° C. for3 hours, then the catalysts were reduced in-situ at 300° C. for 3 hoursin a 10% H₂/N₂ feed.

[0240] Catalyst Testing Conditions

[0241] Catalysts were tested in a fixed bed reactor. Approximately 0.15g of catalyst was weighed and mixed with an equivalent mass of SiC. Themixture was loaded into a reactor and heated to reaction temperature.Reaction gases were delivered via mass flow controllers (Brooks) withwater introduced with a metering pump (Quizix). The composition of thereaction mixture was as follows: H₂ 50%, CO 10%, CO₂ 10%, and H₂O 30%.The reactant mixture was passed through a pre-heater before contactingthe catalyst bed. Following reaction, the product gases were analyzedusing a micro gas chromatograph (Varian Instruments, or Shimadzu).Compositional data on the performance diagram (FIG. 7) is on a dry basiswith water removed.

[0242] Testing Results

[0243]FIG. 7 shows the CO composition in the product stream followingthe scale-up testing at a gas hour space velocity of 50,000 h⁻¹. TABLE 3Catalyst Compositions (mass ratio) Row Col Support Pt Co Rh K Mo V Fe A1 0.9095 0.06 0.005 0.0005 0.025 0 0 0 A 2 0.909 0.06 0.005 0.001 0.0250 0 0 A 3 0.9045 0.06 0.01 0.0005 0.025 0 0 0 A 4 0.904 0.06 0.01 0.0010.025 0 0 0 A 5 0.8995 0.06 0.015 0.0005 0.025 0 0 0 A 6 0.899 0.060.015 0.001 0.025 0 0 0 B 1 0.9095 0.06 0 0.0005 0.025 0.005 0 0 B 20.909 0.06 0 0.001 0.025 0.005 0 0 B 3 0.9045 0.06 0 0.0005 0.025 0.01 00 B 4 0.904 0.06 0 0.001 0.025 0.01 0 0 B 5 0.8995 0.06 0 0.0005 0.0250.015 0 0 B 6 0.899 0.06 0 0.001 0.025 0.015 0 0 C 1 0.9135 0.06 00.0005 0.025 0 0.001 0 C 2 0.913 0.06 0 0.001 0.025 0 0.001 0 C 3 0.91250.06 0 0.0005 0.025 0 0.002 0 C 4 0.912 0.06 0 0.001 0.025 0 0.002 0 C 50.9115 0.06 0 0.0005 0.025 0 0.003 0 C 6 0.911 0.06 0 0.001 0.025 00.003 0 D 1 0.9095 0.06 0 0.0005 0.025 0 0 0.005 D 2 0.909 0.06 0 0.0010.025 0 0 0.005 D 3 0.9045 0.06 0 0.0005 0.025 0 0 0.01 D 4 0.904 0.06 00.001 0.025 0 0 0.01 D 5 0.8995 0.06 0 0.0005 0.025 0 0 0.015 D 6 0.8990.06 0 0.001 0.025 0 0 0.015

Example 8

[0244] Scale-up catalyst samples were prepared by using incipientwetness impregnation of 0.75 grams of ZrO₂ support (Norton, 80-120 mesh)which had been weighed into a 10-dram vial. Aqueous metal precursor saltsolutions were then added in the order: Rh, Co, Fe, Mo, V, Pt, andfinally Na. The precursor salt solutions were tetraammineplatinum (II)hydroxide solution (9.09 % Pt (w/w)), rhodium (III) nitrate (1.0% Rh(w/w)), cobalt (II) nitrate (1.0M), molydbic acid (1.0M), vanadiumcitrate (1.0M), iron (III) nitrate (1.0M), and sodium hydroxide (3.0 N).All starting reagents were nominally research grade from Aldrich, Strem,or Alfa. Following each metal addition, the catalysts were dried at 80°C. overnight and then calcined in air as follows: After Pt addition 300° C. for 3 hours After Rh, Co, or Fe addition 450 ° C. for 3 hours AfterMo or V addition 350 ° C. for 3 hours.

[0245] Following Na addition, the catalysts were calcined at 300° C. for3 hours, then the catalysts were reduced in-situ at 300° C. for 3 hoursin a 10% H₂/N₂ feed.

[0246] Catalyst Testing Conditions

[0247] Catalysts were tested in a fixed bed reactor. Approximately 0.15g of catalyst was weighed and mixed with an equivalent mass of SiC. Themixture was loaded into a reactor and heated to reaction temperature.Reaction gases were delivered via mass flow controllers (Brooks) withwater introduced with a metering pump (Quizix). The composition of thereaction mixture was as follows: H₂ 50%, CO 10%, CO₂ 10%, and H₂O 30%.The reactant mixture was passed through a pre-heater before contactingthe catalyst bed. Following reaction, the product gases were analyzedusing a micro gas chromatograph (Varian Instruments, or Shimadzu).Compositional data on the performance diagrams (FIGS. 10A-10C) is on adry basis with water removed.

[0248] Testing Results

[0249]FIGS. 10A-10C show the CO composition in the product streamfollowing the scale-up testing at a gas hour space velocity of 50,000h⁻¹. TABLE 4 Catalyst Compositions (mass ratio) Row Col ZrO2 Co Water RhPt Na Fe Mo V A 1 90.90 0.50 0.00 0.10 6.00 2.50 0.00 0.00 0.00 A 290.80 0.50 0.00 0.20 6.00 2.50 0.00 0.00 0.00 A 3 90.40 1.00 0.00 0.106.00 2.50 0.00 0.00 0.00 A 4 90.30 1.00 0.00 0.20 6.00 2.50 0.00 0.000.00 B 1 90.90 0.00 0.00 0.10 6.00 2.50 0.50 0.00 0.00 B 2 90.80 0.000.00 0.20 6.00 2.50 0.50 0.00 0.00 B 3 90.40 0.00 0.00 0.10 6.00 2.501.00 0.00 0.00 B 4 90.30 0.00 0.00 0.20 6.00 2.50 1.00 0.00 0.00 C 190.90 0.00 0.00 0.10 6.00 2.50 0.00 0.50 0.00 C 2 90.80 0.00 0.00 0.206.00 2.50 0.00 0.50 0.00 C 3 90.40 0.00 0.00 0.10 6.00 2.50 0.00 1.000.00 C 4 90.30 0.00 0.00 0.20 6.00 2.50 0.00 1.00 0.00 D 1 90.40 0.000.00 0.10 6.00 2.50 0.00 0.00 1.00 D 2 90.30 0.00 0.00 0.20 6.00 2.500.00 0.00 1.00 D 3 89.40 0.00 0.00 0.10 6.00 2.50 0.00 0.00 2.00 D 489.30 0.00 0.00 0.20 6.00 2.50 0.00 0.00 2.00

Example 9

[0250] Scale-up catalyst samples were prepared by using incipientwetness impregnation of 0.75 grams of ZrO₂ support (Norton, 80-120 mesh)which had been weighed into a 10-dram vial. Aqueous metal precursor saltsolutions were then added in the order: Rh, Co, Fe, Mo, V, and Pt. Theprecursor salt solutions were tetraammineplatinum (II) hydroxidesolution (9.09% Pt (w/w)), rhodium (III) nitrate (1.0% Rh (w/w)), cobalt(II) nitrate (1.0M), molydbic acid (1.0M), vanadium citrate (1.0M), andiron (III) nitrate (1.0M). All starting reagents were nominally researchgrade from Aldrich, Strem, or Alfa. Following each metal addition, thecatalysts were dried at 80° C. overnight and then calcined in air asfollows: After Pt addition 300 ° C. for 3 hours After Rh, Co, or Feaddition 450 ° C. for 3 hours After Mo or V addition 350 ° C. for 3hours.

[0251] Following the final addition, the catalysts were reduced in-situat 300° C. for 3 hours in a 10% H₂/N₂ feed.

[0252] Catalyst Testing Conditions

[0253] Catalysts were tested in a fixed bed reactor. Approximately 0.15g of catalyst was weighed and mixed with an equivalent mass of SiC. Themixture was loaded into a reactor and heated to reaction temperature.Reaction gases were delivered via mass flow controllers (Brooks) withwater introduced with a metering pump (Quizix). The composition of thereaction mixture was as follows: H₂ 50%, CO 10%, CO₂ 10%, and H₂O 30%.The reactant mixture was passed. through a pre-heater before contactingthe catalyst bed. Following reaction, the product gases were analyzedusing a micro gas chromatograph (Varian Instruments, or Shimadzu).Compositional data on the performance diagrams (FIGS. 11A and 11B) is ona dry basis with water removed.

[0254] Testing Results

[0255]FIGS. 11A and 11B show the CO composition in the product streamfollowing the scale-up testing at a gas hour space velocity of 50,000h⁻¹. TABLE 5 Catalyst Compositions (mass ratio) Row Col ZrO2 Co Water RhPt Fe Mo V B 3 92.90 0.00 0.00 0.10 6.00 1.00 0.00 0.00 B 4 92.80 0.000.00 0.20 6.00 1.00 0.00 0.00 C 1 93.40 0.00 0.00 0.10 6.00 0.00 0.500.00 C 2 93.30 0.00 0.00 0.20 6.00 0.00 0.50 0.00 C 3 92.90 0.00 0.000.10 6.00 0.00 1.00 0.00 C 4 92.80 0.00 0.00 0.20 6.00 0.00 1.00 0.00 D1 92.90 0.00 0.00 0.10 6.00 0.00 0.00 1.00 D 2 92.80 0.00 0.00 0.20 6.000.00 0.00 1.00 D 3 91.90 0.00 0.00 0.10 6.00 0.00 0.00 2.00 D 4 91.800.00 0.00 0.20 6.00 0.00 0.00 2.00

[0256] Pt1.0%/ Zr R C COCONV H2OCONV CO2PROD CO2PERPROD CH4PROD O2_stdCoNO32 FeNO32 GeOX2 H2MoO4 real real real real real real real real realreal real real Temperature: 300 C. 1 1 25.8564 17.3624 0.9641 34.85240.1872 0.1275 0 0 0 0 1 2 −3.5288 −1.0034 0.0465 1.6792 0.0188 0 0 0 0 01 3 −3.2594 −1.1661 0.0166 0.5998 0.0121 0 0 0 0 0 1 4 −2.9732 −3.72320.008 0.2881 0.0087 0 0 0 0 0 1 5 −2.8279 −4.1686 −0.0176 −0.636 0.00370 0 0 0 0 1 6 −0.8995 −1.8273 0.0207 0.7469 0.007 0 0 0 0 0 1 7 29.892915.3753 0.9475 34.2529 0.1713 0.1275 0 0 0 0 1 8 0.2455 −0.7786 0.03641.317 0.0059 0 0 0 0 0 1 9 1.8628 1.8933 0.0797 2.8821 0.0104 0 0 0 0 01 10 −1.0457 −1.7441 −0.0214 −0.7745 0.0034 0 0 0 0 0 1 11 −0.9415−1.632 −0.0272 −0.9819 −0.0032 0 0 0 0 0 1 12 −1.4473 −2.099 −0.0436−1.5778 −0.0067 0 0 0 0 0 1 13 29.7322 15.3824 0.922 33.3294 0.15120.1275 0 0 0 0 1 14 −0.4246 −0.0063 −0.0224 −0.8114 −0.005 0 0 0 0 0 115 −0.9697 −0.7029 −0.0374 −1.3523 −0.0056 0 0 0 0 0 1 16 32.251115.0975 0.9551 34.5247 0.1837 0.1275 0 0 0 0 2 1 25.7402 15.132 0.82129.6779 0.1024 0 0 1 0 0 2 2 23.6205 13.0894 0.7368 26.6334 0.0932 0 0 10 0 2 3 22.2339 13.8399 0.7116 25.7223 0.0904 0 0 1 0 0 2 4 10.27886.0504 0.3053 11.0365 0.0334 0 0 1 0 1 2 5 24.8097 18.3968 0.758627.4246 0.0984 0 1 1 0 0 2 6 30.7805 17.4659 0.9424 34.0689 0.1445 0 0 00 0 2 7 24.5818 17.5787 0.7641 27.6231 0.1029 0 0 0 0 0 2 8 30.048318.2382 1.0024 36.2373 0.1267 0 0 0 0 0 2 9 8.9325 5.5702 0.275 9.93970.0302 0 0 0 0 1 2 10 48.0297 −3.6479 0.6535 23.6248 0.5638 0 1 0 0 0 211 33.7357 12.0981 0.8374 30.2711 0.2395 0 0 0 0 0 2 12 25.0185 12.51030.7266 26.268 0.133 0 0 0 0 0 2 13 32.2828 17.7494 1.0157 36.7159 0.1480 0 0 0 0 2 14 14.7003 10.1762 0.4613 16.6741 0.0611 0 0 0 0 1 2 1540.8678 6.002 0.8233 29.7614 0.3924 0 1 0 0 0 2 16 −0.6906 −1.1865−0.0214 −0.7728 −0.0011 0 0 0 0 0 3 1 25.0677 15.2287 0.7962 28.7810.0976 0 0 0.875 0 0 3 2 21.7886 14.5137 0.6935 25.0715 0.0867 0 0 0.8750 0 3 3 23.5288 15.7457 0.7124 25.7537 0.0872 0 0 0.875 0 0 3 4 10.78357.3033 0.3034 10.9679 0.0327 0 0 0.875 0 0.875 3 5 35.9677 7.7821 0.809529.2621 0.2747 0 0.875 0.875 0 0 3 6 29.594 18.255 0.8479 30.6516 0.13060 0 0 0 0 3 7 27.2904 16.7775 0.7916 28.6165 0.117 0 0 0 0 0 3 8 32.075921.3168 1.0149 36.687 0.1287 0 0 0 0 0 3 9 11.3167 8.9989 0.3238 11.70440.0337 0 0 0 0 0.875 3 10 47.8794 1.867 0.6668 24.1028 0.5212 0 0.875 00 0 3 11 38.1087 10.0964 0.8129 29.3858 0.2958 0 0 0 0 0 3 12 29.108712.0353 0.731 26.4253 0.167 0 0 0 0 0 3 13 32.9772 21.6736 1.001 36.18590.1453 0 0 0 0 0 3 14 26.1774 17.2847 0.7394 26.7277 0.0884 0 0 0 00.875 3 15 44.0139 7.4653 0.7942 28.7088 0.4053 0 0.875 0 0 0 3 163.3654 3.7276 0.0426 1.5406 −0.0027 0 0 0 0 0 4 1 25.492 16.5937 0.763427.5979 0.0911 0 0 0.75 0 0 4 2 25.0526 16.4405 0.7271 26.2844 0.0861 00 0.75 0 0 4 3 26.6439 16.1513 0.7463 26.977 0.0889 0 0 0.75 0 0 4 48.939 4.4471 0.1855 6.7042 0.0195 0 0 0.75 0 0.75 4 5 31.3599 14.45630.7785 28.1423 0.1927 0 0.75 0.75 0 0 4 6 32.6696 17.1698 0.8987 32.48740.1475 0 0 0 0 0 4 7 31.6017 13.1545 0.7725 27.9266 0.1942 0 0 0 0 0 4 833.4823 19.718 1.0123 36.5929 0.1326 0 0 0 0 0 4 9 12.4995 6.3069 0.37513.5551 0.046 0 0 0 0 0.75 4 10 48.6152 −4.3375 0.6394 23.115 0.5697 00.75 0 0 0 4 11 42.989 5.7041 0.7377 26.6675 0.3792 0 0 0 0 0 4 1232.6771 8.7176 0.7127 25.7625 0.245 0 0 0 0 0 4 13 35.464 14.8498 0.957834.6247 0.2053 0 0 0 0 0 4 14 24.0107 14.9324 0.72 26.0278 0.0894 0 0 00 0.75 4 15 39.2751 8.6633 0.8092 29.2522 0.319 0 0.75 0 0 0 4 16 31.80615.0401 0.8979 32.4605 0.1745 0.1275 0 0 0 0 5 1 26.262 16.477 0.729326.3635 0.088 0 0 0.625 0 0 5 2 23.9323 15.5571 0.7185 25.9736 0.0827 00 0.625 0 0 5 3 25.3808 16.1474 0.7857 28.403 0.0965 0 0 0.625 0 0 5 49.1171 4.2487 0.2386 8.6247 0.0208 0 0 0.625 0 0.625 5 5 26.6273 17.45910.8121 29.3586 0.1114 0 0.625 0.625 0 0 5 6 32.4494 18.2364 0.892432.2599 0.1711 0 0 0 0 0 5 7 40.5821 7.1924 0.6488 23.4554 0.3589 0 0 00 0 5 8 32.5308 20.5892 0.9922 35.8668 0.1299 0 0 0 0 0 5 9 18.031715.0408 0.5278 19.0801 0.0576 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0.7471 27.007 0.2395 0 0.375 0 0 0 7 16 34.1815 15.67620.9132 33.013 0.1882 0.1275 0 0 0 0 8 1 24.3356 15.0031 0.7199 26.02560.0889 0 0 0.25 0 0 8 2 24.501 16.4553 0.7674 27.7415 0.097 0 0 0.25 0 08 3 26.1797 15.4862 0.7758 28.0436 0.0977 0 0 0.25 0 0 8 4 23.902313.5114 0.6887 24.8975 0.0864 0 0 0.25 0 0.25 8 5 27.2773 16.1215 0.815829.4917 0.1019 0 0.25 0.25 0 0 8 6 43.6154 1.6883 0.7068 25.5505 0.43040 0 0 0 0 8 7 54.0389 −18.2872 0.2857 10.327 0.768 0 0 0 0 0 8 8 32.232719.5627 0.9111 32.9365 0.1482 0 0 0 0 0 8 9 29.5791 16.0012 0.847330.6296 0.1394 0 0 0 0 0.25 8 10 49.7662 −9.2035 0.5443 19.6769 0.6038 00.25 0 0 0 8 11 48.2982 −7.9653 0.5573 20.1458 0.566 0 0 0 0 0 8 1243.5519 −1.5649 0.5715 20.6589 0.4762 0 0 0 0 0 8 13 42.773 7.99630.7849 28.3752 0.3819 0 0 0 0 0 8 14 31.8568 17.6636 0.8855 32.01020.1807 0 0 0 0 0.25 8 15 35.8667 9.7526 0.7675 27.7441 0.275 0 0.25 0 00 8 16 1.3994 3.1514 −0.006 −0.2176 −0.0045 0 0 0 0 0 9 1 18.333111.0666 0.5484 19.8255 0.0638 0 0 0.25 0.2 0 9 2 22.798 15.9195 0.697725.2221 0.0827 0 0 0.4375 0 0 9 3 13.6014 15.3552 0.3517 12.7144 0.03120 0 0.625 0 0 9 4 28.351 21.8465 0.8623 31.1733 0.1033 0 0 0.8125 0 0 95 29.4335 21.2793 0.9293 33.5925 0.1106 0 1 1 0 0 9 6 21.2667 16.57140.5955 21.5278 0.0682 0 0 0 0.2 0 9 7 25.3599 18.0756 0.7027 25.4020.0854 0 0 0 0 0 9 8 21.966 14.7363 0.6219 22.481 0.0736 0 0 0 0 0 9 931.1704 19.4661 0.8974 32.4422 0.1305 0 0 0 0 0 9 10 31.8494 19.29230.9109 32.9279 0.1397 0 1 0 0 0 9 11 17.0166 13.0969 0.4865 17.58820.051 0 0 0 0.2 0 9 12 25.0631 16.8801 0.7186 25.9785 0.0869 0 0 0 0 0 913 19.9114 13.2859 0.5459 19.7345 0.0645 0 0 0 0 0 9 14 31.5204 18.40060.8541 30.874 0.1476 0 0 0 0 0 9 15 34.16 17.1821 0.8661 31.3099 0.19050 1 0 0 0 9 16 2.7882 4.2082 0.0005 0.0192 −0.0095 0 0 0 0 0 10 120.1799 15.6023 0.5626 20.3382 0.0639 0 0 0.25 0.1786 0 10 2 23.858416.4225 0.6988 25.2598 0.0823 0 0 0.4375 0 0 10 3 15.4388 11.8361 0.427715.4606 0.0438 0 0 0.625 0 0 10 4 29.1664 21.6823 0.8605 31.1062 0.09990 0 0.8125 0 0 10 5 29.7657 20.4923 0.893 32.2799 0.1072 0 0.8929 1 0 010 6 22.18 16.7809 0.6181 22.3455 0.0709 0 0 0 0.1786 0 10 7 26.896418.4335 0.7687 27.7879 0.0978 0 0 0 0 0 10 8 22.7626 17.3084 0.629822.7655 0.0704 0 0 0 0 0 10 9 31.0541 20.3764 0.8791 31.7796 0.1285 0 00 0 0 10 10 31.5314 20.1611 0.8887 32.1276 0.1379 0 0.8929 0 0 0 10 1118.497 14.278 0.5299 19.1546 0.054 0 0 0 0.1786 0 10 12 27.0928 17.55180.777 28.0886 0.1001 0 0 0 0 0 10 13 23.9418 16.8238 0.6968 25.18850.0802 0 0 0 0 0 10 14 32.8367 16.8366 0.8584 31.0301 0.1726 0 0 0 0 010 15 35.3845 16.154 0.8552 30.9151 0.2129 0 0.8929 0 0 0 10 16 32.492416.3973 0.857 30.9802 0.1675 0.1275 0 0 0 0 11 1 17.8706 12.5355 0.53919.4849 0.0583 0 0 0.25 0.1571 0 11 2 22.1385 14.6388 0.6381 23.06780.0756 0 0 0.4375 0 0 11 3 16.2493 9.7877 0.4863 17.5787 0.0511 0 00.625 0 0 11 4 28.4408 19.613 0.8619 31.1555 0.1022 0 0 0.8125 0 0 11 528.7788 20.3358 0.8639 31.2296 0.1008 0 0.7857 1 0 0 11 6 21.334115.2564 0.5892 21.2992 0.0673 0 0 0 0.1571 0 11 7 27.2565 17.5295 0.799128.886 0.1046 0 0 0 0 0 11 8 22.8741 15.5232 0.6559 23.7095 0.0754 0 0 00 0 11 9 31.075 18.1195 0.917 33.1497 0.1331 0 0 0 0 0 11 10 31.377118.8457 0.8762 31.6749 0.1522 0 0.7857 0 0 0 11 11 21.3374 14.18230.6491 23.4647 0.0785 0 0 0 0.1571 0 11 12 25.5254 16.7175 0.76 27.47440.1037 0 0 0 0 0 11 13 20.9039 14.4462 0.64 23.1367 0.0754 0 0 0 0 0 1114 33.7178 14.9458 0.8333 30.1232 0.2011 0 0 0 0 0 11 15 34.0506 15.34720.8472 30.6271 0.2145 0 0.7857 0 0 0 11 16 0.2666 0.8625 −0.0072 −0.2617−0.0041 0 0 0 0 0 12 1 18.4252 12.5906 0.6282 22.7083 0.0734 0 0 0.250.1357 0 12 2 21.4727 15.7898 0.6968 25.1879 0.0852 0 0 0.4375 0 0 12 314.1262 12.3376 0.4687 16.9417 0.0497 0 0 0.625 0 0 12 4 26.6361 19.84490.8375 30.2751 0.0896 0 0 0.8125 0 0 12 5 26.1247 23.2018 0.7532 27.22640.0813 0 0.6786 1 0 0 12 6 25.9088 17.9446 0.7612 27.5175 0.0905 0 0 00.1357 0 12 7 25.573 24.4683 0.7131 25.7792 0.0985 0 0 0 0 0 12 8 24.26217.1356 0.7712 27.8785 0.0918 0 0 0 0 0 12 9 29.8063 15.9041 0.871231.4939 0.1526 0 0 0 0 0 12 10 34.0875 13.806 0.859 31.0513 0.2288 00.6786 0 0 0 12 11 23.2764 16.0656 0.7007 25.3292 0.0852 0 0 0 0.1357 012 12 26.9347 14.5078 0.7474 27.0175 0.115 0 0 0 0 0 12 13 25.073914.2758 0.813 29.3912 0.1076 0 0 0 0 0 12 14 34.2818 9.7762 0.833930.1465 0.2607 0 0 0 0 0 12 15 35.628 9.6941 0.8181 29.5727 0.2742 00.6786 0 0 0 12 16 0.8243 0.262 0.0134 0.4858 −0.0025 0 0 0 0 0 13 118.3427 17.1145 0.5463 19.7493 0.0541 0 0 0.25 0.1143 0 13 2 21.395819.2387 0.599 21.6519 0.063 0 0 0.4375 0 0 13 3 15.8656 13.3135 0.44916.2312 0.0452 0 0 0.625 0 0 13 4 27.8323 18.0095 0.8182 29.5764 0.09820 0 0.8125 0 0 13 5 27.6816 18.912 0.8077 29.1984 0.0936 0 0.5714 1 0 013 6 26.0154 20.0225 0.8041 29.0693 0.0909 0 0 0 0.1143 0 13 7 27.32117.8397 0.8275 29.9151 0.1259 0 0 0 0 0 13 8 25.8111 17.8768 0.765827.6837 0.0907 0 0 0 0 0 13 9 32.5862 15.9816 0.7969 28.8078 0.1975 0 00 0 0 13 10 41.3818 4.9336 0.7015 25.3603 0.3954 0 0.5714 0 0 0 13 1124.8301 17.6776 0.6894 24.9214 0.0831 0 0 0 0.1143 0 13 12 26.843715.7759 0.7715 27.8911 0.1353 0 0 0 0 0 13 13 24.7873 17.0919 0.75127.1481 0.0946 0 0 0 0 0 13 14 34.4795 12.7622 0.74 26.7515 0.2396 0 0 00 0 13 15 36.4404 11.2958 0.7768 28.0793 0.2677 0 0.5714 0 0 0 13 1632.5622 16.8288 0.7849 28.3746 0.1755 0.1275 0 0 0 0 14 1 20.256712.3853 0.6712 24.2633 0.0852 0 0 0.25 0.0929 0 14 2 22.68 15.59790.7275 26.2996 0.0862 0 0 0.4375 0 0 14 3 17.0763 12.9293 0.5885 21.2730.0675 0 0 0.625 0 0 14 4 26.0405 18.4515 0.8042 29.07 0.1036 0 0 0.81250 0 14 5 26.0927 19.3723 0.7707 27.8589 0.0941 0 0.4643 1 0 0 14 624.2827 16.6636 0.7693 27.8114 0.0989 0 0 0 0.0929 0 14 7 27.819515.8631 0.8198 29.6364 0.1473 0 0 0 0 0 14 8 26.9972 16.5785 0.807629.1956 0.11 0 0 0 0 0 14 9 38.8468 6.9959 0.7191 25.9951 0.3418 0 0 0 00 14 10 48.9533 −4.4406 0.5294 19.1373 0.5957 0 0.4643 0 0 0 14 1124.6424 16.8798 0.7738 27.9708 0.1041 0 0 0 0.0929 0 14 12 28.140713.399 0.7724 27.9235 0.1621 0 0 0 0 0 14 13 27.1547 16.2099 0.759327.4492 0.1341 0 0 0 0 0 14 14 36.8809 8.2728 0.6993 25.2804 0.3112 0 00 0 0 14 15 36.4174 8.3339 0.7383 26.6874 0.3082 0 0.4643 0 0 0 14 161.1257 0.8364 −0.0533 −1.9279 −0.0116 0 0 0 0 0 15 1 19.9305 15.95560.6162 22.277 0.071 0 0 0.25 0.0714 0 15 2 22.3009 14.3322 0.743 26.86050.0864 0 0 0.4375 0 0 15 3 18.8732 13.6249 0.6143 22.2054 0.0672 0 00.625 0 0 15 4 24.0558 15.8686 0.7818 28.2606 0.103 0 0 0.8125 0 0 15 525.927 17.3231 0.7769 28.0848 0.0937 0 0.3571 1 0 0 15 6 26.5932 17.83760.8142 29.4341 0.1077 0 0 0 0.0714 0 15 7 29.5785 15.1647 0.8206 29.66530.2062 0 0 0 0 0 15 8 27.0224 17.6058 0.8195 29.6227 0.1215 0 0 0 0 0 159 45.5964 −1.427 0.6094 22.031 0.5239 0 0 0 0 0 15 10 47.7892 −4.82840.5902 21.3358 0.5789 0 0.3571 0 0 0 15 11 27.2611 16.2992 0.784 28.34220.1126 0 0 0 0.0714 0 15 12 30.9992 12.5497 0.7158 25.8775 0.2007 0 0 00 0 15 13 31.8053 9.9612 0.7893 28.5319 0.2159 0 0 0 0 0 15 14 37.38245.9023 0.7393 26.7266 0.3762 0 0 0 0 0 15 15 38.1161 5.5222 0.69825.2309 0.3851 0 0.3571 0 0 0 15 16 0.8754 0.7034 −0.0221 −0.7984−0.0015 0 0 0 0 0 16 1 5.642 6.3495 0.1244 4.4983 0.0117 0 0 0.25 0.05 016 2 20.1376 15.5842 0.6325 22.8636 0.0761 0 0 0.4375 0 0 16 3 17.7215.0247 0.5638 20.3814 0.0668 0 0 0.625 0 0 16 4 20.745 16.5113 0.676824.4663 0.0809 0 0 0.8125 0 0 16 5 23.4069 16.7755 0.7548 27.2856 0.09510 0.25 1 0 0 16 6 28.4013 17.264 0.8013 28.9677 0.1431 0 0 0 0.05 0 16 734.7081 11.4293 0.7565 27.3464 0.2707 0 0 0 0 0 16 8 31.5206 15.05940.7868 28.4425 0.1976 0 0 0 0 0 16 9 50.5474 −10.4983 0.4745 17.15190.6572 0 0 0 0 0 16 10 53.9071 −15.5894 0.3503 12.6648 0.7563 0 0.25 0 00 16 11 28.0202 14.2589 0.7625 27.5636 0.156 0 0 0 0.05 0 16 12 37.4585−1.0934 0.6168 22.2983 0.4116 0 0 0 0 0 16 13 38.0537 −0.1529 0.589721.3174 0.4244 0 0 0 0 0 16 14 43.3047 −5.8456 0.4632 16.7442 0.5402 0 00 0 0 16 15 43.8393 −6.2457 0.4623 16.7117 0.5811 0 0.25 0 0 0 16 1631.5947 17.1493 0.9526 34.4377 0.162 0.1275 0 0 0 0 Temperature: 350 C.1 1 26.6121 4.2313 0.5077 18.1105 0.2508 0.1275 0 0 0 0 1 2 0.7229−0.0412 0.019 0.6786 0.0037 0 0 0 0 0 1 3 0.1711 0.8278 −0.0091 −0.3252−0.0032 0 0 0 0 0 1 4 −0.908 0.1406 −0.0264 −0.943 −0.0045 0 0 0 0 0 1 5−0.7495 0.836 −0.0283 −1.0102 −0.0058 0 0 0 0 0 1 6 2.4441 1.7805 0.0682.4241 0.0064 0 0 0 0 0 1 7 28.9966 3.751 0.6072 21.6574 0.2614 0.1275 00 0 0 1 8 2.0242 0.7457 0.0535 1.9071 0.0052 0 0 0 0 0 1 9 2.9343 4.38740.0851 3.0351 0.0069 0 0 0 0 0 1 10 −0.1488 −0.8318 −0.0195 −0.6938−0.0019 0 0 0 0 0 1 11 0.7994 2.1609 0.0017 0.0598 −0.0035 0 0 0 0 0 112 −0.632 2.4348 −0.0385 −1.3723 −0.0098 0 0 0 0 0 1 13 26.1795 5.9880.5864 20.9167 0.2146 0.1275 0 0 0 0 1 14 −0.2602 1.2811 −0.0335 −1.1961−0.0087 0 0 0 0 0 1 15 −0.6717 −1.2437 −0.0382 −1.3614 −0.0079 0 0 0 0 01 16 31.5724 1.824 0.5405 19.2785 0.3239 0.1275 0 0 0 0 2 1 17.084115.4021 0.56 19.9736 0.0661 0 0 1 0 0 2 2 18.0063 12.9874 0.5891 21.01390.0698 0 0 1 0 0 2 3 15.0803 15.251 0.4847 17.2892 0.0549 0 0 1 0 0 2 44.4842 8.1302 0.1158 4.1317 0.0078 0 0 1 0 1 2 5 17.2844 12.8567 0.566920.2224 0.0786 0 1 1 0 0 2 6 25.9509 10.3813 0.642 22.9003 0.1951 0 0 00 0 2 7 20.65 11.2507 0.5812 20.7331 0.1276 0 0 0 0 0 2 8 21.447412.8711 0.6705 23.9149 0.0945 0 0 0 0 0 2 9 3.6449 1.9165 0.1037 3.69760.0136 0 0 0 0 1 2 10 34.8724 −0.4665 0.4245 15.1434 0.4166 0 1 0 0 0 211 36.7992 −0.2947 0.4115 14.6794 0.442 0 0 0 0 0 2 12 24.1156 6.4410.4378 15.618 0.2335 0 0 0 0 0 2 13 24.9384 10.9649 0.6234 22.23770.1666 0 0 0 0 0 2 14 8.5274 4.439 0.2624 9.359 0.0342 0 0 0 0 1 2 1528.6142 4.9078 0.5576 19.8878 0.278 0 1 0 0 0 2 16 −0.9584 −1.5171−0.0252 −0.8998 −0.0047 0 0 0 0 0 3 1 15.8468 12.4486 0.5471 19.51520.0659 0 0 0.875 0 0 3 2 15.5947 16.5628 0.5001 17.8378 0.0533 0 0 0.8750 0 3 3 16.0961 14.7791 0.5281 18.8373 0.0615 0 0 0.875 0 0 3 4 5.179.7616 0.1347 4.8032 0.0081 0 0 0.875 0 0.875 3 5 20.5579 12.0007 0.556619.8525 0.1333 0 0.875 0.875 0 0 3 6 26.1452 9.8078 0.655 23.3632 0.1920 0 0 0 0 3 7 23.2198 8.8504 0.6154 21.9527 0.1619 0 0 0 0 0 3 8 21.157418.5925 0.6706 23.9191 0.1001 0 0 0 0 0 3 9 3.7143 0.7242 0.1444 5.15040.0214 0 0 0 0 0.875 3 10 37.747 −2.5078 0.5026 17.9292 0.4503 0 0.875 00 0 3 11 41.9429 −7.1208 0.4134 14.7469 0.5312 0 0 0 0 0 3 12 28.27393.7031 0.437 15.5872 0.3017 0 0 0 0 0 3 13 28.3874 10.9515 0.719725.6724 0.1986 0 0 0 0 0 3 14 14.9962 10.1421 0.4954 17.6719 0.065 0 0 00 0.875 3 15 31.6362 2.8859 0.5904 21.0596 0.3145 0 0.875 0 0 0 3 160.0293 −0.2006 −0.008 −0.2849 0.0015 0 0 0 0 0 4 1 16.427 9.6501 0.566120.1935 0.0728 0 0 0.75 0 0 4 2 15.221 15.321 0.5108 18.2185 0.0607 0 00.75 0 0 4 3 19.7181 12.3922 0.6592 23.5147 0.0854 0 0 0.75 0 0 4 44.1167 5.5585 0.0614 2.1893 0.0054 0 0 0.75 0 0.75 4 5 19.3913 11.29330.6021 21.4763 0.1113 0 0.75 0.75 0 0 4 6 27.8954 9.9996 0.6594 23.52040.2203 0 0 0 0 0 4 7 28.0012 3.3779 0.507 18.0839 0.2824 0 0 0 0 0 4 824.0928 14.3242 0.7318 26.1039 0.1243 0 0 0 0 0 4 9 4.3545 6.5735 0.10313.6788 0.0119 0 0 0 0 0.75 4 10 40.5602 −7.7433 0.3686 13.1472 0.5263 00.75 0 0 0 4 11 45.3668 −11.3176 0.2757 9.835 0.6384 0 0 0 0 0 4 1234.4061 −1.7401 0.3998 14.2626 0.4243 0 0 0 0 0 4 13 33.4356 4.99560.5357 19.1077 0.3461 0 0 0 0 0 4 14 12.9059 8.8004 0.4174 14.89 0.05390 0 0 0 0.75 4 15 30.3742 2.0829 0.562 20.0449 0.304 0 0.75 0 0 0 4 1627.3051 3.9656 0.5117 18.253 0.2615 0.1275 0 0 0 0 5 1 15.4631 9.90590.5312 18.9484 0.0679 0 0 0.625 0 0 5 2 16.9891 10.757 0.5687 20.28660.0731 0 0 0.625 0 0 5 3 16.7332 14.809 0.5628 20.0763 0.069 0 0 0.625 00 5 4 4.2413 0.5825 0.202 7.2068 0.0341 0 0 0.625 0 0.625 5 5 16.736815.5641 0.5465 19.4924 0.0764 0 0.625 0.625 0 0 5 6 30.7992 5.37540.6441 22.9759 0.288 0 0 0 0 0 5 7 36.572 −4.5773 0.4586 16.3571 0.45030 0 0 0 0 5 8 23.8959 12.2729 0.7452 26.5801 0.1321 0 0 0 0 0 5 9 9.12589.806 0.292 10.4141 0.0352 0 0 0 0 0.625 5 10 38.9759 −9.0948 0.417314.8845 0.5028 0 0.625 0 0 0 5 11 47.8059 −17.9847 0.2779 9.9113 0.69350 0 0 0 0 5 12 37.6722 −10.2117 0.3922 13.9881 0.4952 0 0 0 0 0 5 1334.0163 4.753 0.6191 22.0845 0.3474 0 0 0 0 0 5 14 17.6158 13.86970.5551 19.7988 0.0806 0 0 0 0 0.625 5 15 31.1363 −1.3651 0.6396 22.81490.309 0 0.625 0 0 0 5 16 1.9025 0.6739 0.0833 2.9712 0.0273 0 0 0 0 0 61 15.9364 4.2583 0.5857 20.8918 0.093 0 0 0.5 0 0 6 2 18.0377 11.84910.5996 21.3885 0.0792 0 0 0.5 0 0 6 3 17.8625 13.0739 0.5751 20.51460.0724 0 0 0.5 0 0 6 4 10.7849 10.4828 0.3501 12.4871 0.0464 0 0 0.5 00.5 6 5 18.9483 8.7248 0.6339 22.6095 0.0918 0 0.5 0.5 0 0 6 6 33.76810.2912 0.595 21.2252 0.3567 0 0 0 0 0 6 7 43.9136 −16.1328 0.305810.9082 0.6268 0 0 0 0 0 6 8 25.2333 8.1653 0.7274 25.9472 0.1604 0 0 00 0 6 9 17.5069 7.8926 0.5625 20.0646 0.0883 0 0 0 0 0.5 6 10 42.0395−12.6294 0.3696 13.1828 0.5676 0 0.5 0 0 0 6 11 48.9676 −20.5759 0.27729.8873 0.7122 0 0 0 0 0 6 12 40.3603 −11.7344 0.2876 10.2595 0.5687 0 00 0 0 6 13 39.5785 −5.8188 0.4669 16.6559 0.491 0 0 0 0 0 6 14 18.595212.5173 0.5505 19.6377 0.1124 0 0 0 0 0.5 6 15 31.2707 −0.048 0.537719.1788 0.3366 0 0.5 0 0 0 6 16 0.5692 −2.7442 0.0169 0.6011 0.0092 0 00 0 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22.1693 0.0856 0 0 0.25 0 0 8 4 16.444412.3897 0.552 19.6888 0.0736 0 0 0.25 0 0.25 8 5 17.419 10.4163 0.576620.5681 0.08 0 0.25 0.25 0 0 8 6 41.5525 −8.8902 0.3588 12.7967 0.5577 00 0 0 0 8 7 46.476 −17.8531 0.1542 5.499 0.705 0 0 0 0 0 8 8 27.24917.0562 0.5925 21.1361 0.2442 0 0 0 0 0 8 9 21.3119 8.2213 0.5753 20.52190.1618 0 0 0 0 0.25 8 10 44.4371 −18.7895 0.3125 11.1452 0.6355 0 0.25 00 0 8 11 49.1009 −22.5282 0.1618 5.7698 0.7568 0 0 0 0 0 8 12 44.4969−16.8927 0.2149 7.6663 0.663 0 0 0 0 0 8 13 45.3275 −12.0025 0.336612.0053 0.6387 0 0 0 0 0 8 14 29.1399 2.7123 0.5626 20.069 0.2911 0 0 00 0.25 8 15 34.5782 −4.8769 0.4912 17.5198 0.4131 0 0.25 0 0 0 8 16−1.2743 −2.7008 −0.03 −1.0688 0.0033 0 0 0 0 0 9 1 11.5083 9.3782 0.408814.5805 0.0537 0 0 0.25 0.2 0 9 2 14.2047 12.4382 0.479 17.0871 0.0606 00 0.4375 0 0 9 3 7.4459 2.7426 0.3219 11.4816 0.0501 0 0 0.625 0 0 9 418.0985 9.7764 0.6565 23.4184 0.0918 0 0 0.8125 0 0 9 5 18.9458 14.7520.6418 22.8938 0.0841 0 1 1 0 0 9 6 13.2875 12.7718 0.4615 16.4614 0.0580 0 0 0.2 0 9 7 16.2231 12.4507 0.548 19.5489 0.0771 0 0 0 0 0 9 813.5706 6.213 0.4808 17.1506 0.0652 0 0 0 0 0 9 9 26.4751 4.5935 0.647523.0961 0.2217 0 0 0 0 0 9 10 25.8073 4.7234 0.6083 21.6975 0.2253 0 1 00 0 9 11 12.4059 6.0539 0.4331 15.4495 0.0592 0 0 0 0.2 0 9 12 15.272610.9813 0.5197 18.5377 0.07 0 0 0 0 0 9 13 11.8369 11.4322 0.408514.5708 0.0476 0 0 0 0 0 9 14 28.2605 6.3523 0.5242 18.6978 0.2872 0 0 00 0 9 15 30.6231 5.5792 0.5352 19.0915 0.3208 0 1 0 0 0 9 16 −0.02584.3078 −0.0052 −0.1849 −0.0032 0 0 0 0 0 10 1 11.039 6.347 0.468216.7007 0.0657 0 0 0.25 0.1786 0 10 2 14.0721 8.8068 0.5481 19.55230.0687 0 0 0.4375 0 0 10 3 9.1083 6.5365 0.3113 11.1035 0.0413 0 0 0.6250 0 10 4 17.4056 11.5802 0.6699 23.8962 0.086 0 0 0.8125 0 0 10 5 19.659.602 0.6818 24.3192 0.091 0 0.8929 1 0 0 10 6 14.7232 7.2897 0.529518.8885 0.071 0 0 0 0.1786 0 10 7 16.629 8.8331 0.5963 21.2701 0.1079 00 0 0 0 10 8 12.7914 7.1486 0.4534 16.1743 0.0625 0 0 0 0 0 10 9 25.45465.0826 0.6132 21.8729 0.2292 0 0 0 0 0 10 10 25.9503 5.5687 0.592721.1404 0.2288 0 0.8929 0 0 0 10 11 12.9761 7.5932 0.4482 15.9859 0.05630 0 0 0.1786 0 10 12 17.4082 8.7968 0.5892 21.0173 0.0984 0 0 0 0 0 1013 15.5878 5.7496 0.5572 19.8751 0.0763 0 0 0 0 0 10 14 31.6303 0.31490.5542 19.7675 0.3436 0 0 0 0 0 10 15 32.0503 1.2431 0.4897 17.46660.3696 0 0.8929 0 0 0 10 16 27.4557 −0.118 0.5274 18.8129 0.2884 0.12750 0 0 0 11 1 10.1403 4.9198 0.4336 15.4667 0.0582 0 0 0.25 0.1571 0 11 213.7097 7.7748 0.5223 18.6314 0.0638 0 0 0.4375 0 0 11 3 8.5048 4.52830.37 13.1978 0.0467 0 0 0.625 0 0 11 4 16.2509 12.108 0.6142 21.90780.0675 0 0 0.8125 0 0 11 5 16.5509 10.4361 0.6059 21.6109 0.0803 00.7857 1 0 0 11 6 12.2348 7.6726 0.4923 17.5611 0.0647 0 0 0 0.1571 0 117 17.5853 6.8906 0.6157 21.961 0.1288 0 0 0 0 0 11 8 13.2999 6.90110.4531 16.1616 0.0599 0 0 0 0 0 11 9 25.1299 3.7023 0.6186 22.06540.2387 0 0 0 0 0 11 10 27.2335 4.2125 0.599 21.368 0.2451 0 0.7857 0 0 011 11 14.5681 7.6756 0.5272 18.8067 0.0658 0 0 0 0.1571 0 11 12 17.76919.1387 0.5894 21.0249 0.109 0 0 0 0 0 11 13 11.9905 9.478 0.5287 18.85880.0673 0 0 0 0 0 11 14 32.4658 0.5299 0.5409 19.2951 0.3667 0 0 0 0 0 1115 31.0779 −2.3001 0.5845 20.8507 0.3615 0 0.7857 0 0 0 11 16 −1.4274−2.7581 −0.0222 −0.7901 −0.0036 0 0 0 0 0 12 1 10.5005 7.0853 0.426215.2036 0.0532 0 0 0.25 0.1357 0 12 2 14.616 9.2859 0.5208 18.57520.0665 0 0 0.4375 0 0 12 3 9.3877 5.3689 0.3591 12.8089 0.0491 0 0 0.6250 0 12 4 18.0691 11.774 0.5965 21.2757 0.0781 0 0 0.8125 0 0 12 515.9035 10.5955 0.6116 21.8157 0.0787 0 0.6786 1 0 0 12 6 14.756 9.99560.5711 20.3722 0.0775 0 0 0 0.1357 0 12 7 20.3739 8.707 0.5664 20.20450.1421 0 0 0 0 0 12 8 16.347 8.9824 0.5447 19.4295 0.0732 0 0 0 0 0 12 926.4262 2.5268 0.6155 21.954 0.266 0 0 0 0 0 12 10 32.3702 1.4648 0.528918.8656 0.3522 0 0.6786 0 0 0 12 11 14.1759 7.667 0.5381 19.1932 0.06870 0 0 0.1357 0 12 12 19.4168 6.3148 0.5762 20.5532 0.1561 0 0 0 0 0 1213 14.4741 9.2631 0.5928 21.1456 0.0835 0 0 0 0 0 12 14 35.5131 −5.1750.4422 15.7744 0.4338 0 0 0 0 0 12 15 33.8652 −6.1037 0.509 18.15470.4315 0 0.6786 0 0 0 12 16 −0.3858 −2.0916 −0.0112 −0.398 0.0016 0 0 00 0 13 1 11.1671 7.3884 0.4586 16.3567 0.0576 0 0 0.25 0.1143 0 13 213.435 9.2774 0.5185 18.4945 0.0645 0 0 0.4375 0 0 13 3 11.9785 9.00530.3386 12.0795 0.0403 0 0 0.625 0 0 13 4 14.153 10.5741 0.5433 19.37840.0715 0 0 0.8125 0 0 13 5 15.2108 8.5049 0.5839 20.8267 0.0788 0 0.57141 0 0 13 6 14.7554 10.004 0.52 18.5488 0.0691 0 0 0 0.1143 0 13 7 19.5029.746 0.5025 17.9225 0.1191 0 0 0 0 0 13 8 14.8409 10.3532 0.494317.6324 0.0585 0 0 0 0 0 13 9 28.9082 1.206 0.5722 20.4092 0.3106 0 0 00 0 13 10 35.8084 −5.3825 0.4505 16.0704 0.4498 0 0.5714 0 0 0 13 1114.6795 8.1249 0.5794 20.6688 0.0744 0 0 0 0.1143 0 13 12 19.6717 7.32270.5748 20.5039 0.1409 0 0 0 0 0 13 13 16.5111 10.606 0.5265 18.77990.0613 0 0 0 0 0 13 14 30.947 −1.2122 0.5206 18.5702 0.3807 0 0 0 0 0 1315 31.9566 −2.8864 0.532 18.975 0.4049 0 0.5714 0 0 0 13 16 26.90670.2947 0.5181 18.4823 0.3005 0.1275 0 0 0 0 14 1 10.5149 6.8603 0.44916.0155 0.0561 0 0 0.25 0.0929 0 14 2 14.7047 10.3856 0.5025 17.92260.0608 0 0 0.4375 0 0 14 3 9.0093 8.1848 0.3854 13.746 0.049 0 0 0.625 00 14 4 13.8408 9.9248 0.5411 19.3028 0.0666 0 0 0.8125 0 0 14 5 15.117610.598 0.5468 19.5044 0.0622 0 0.4643 1 0 0 14 6 13.6028 11.5495 0.500717.8614 0.0573 0 0 0 0.0929 0 14 7 20.7472 6.2939 0.5791 20.6553 0.18560 0 0 0 0 14 8 15.444 8.9189 0.5617 20.0343 0.0721 0 0 0 0 0 14 9 34.665−6.9765 0.4234 15.1028 0.4607 0 0 0 0 0 14 10 41.8002 −12.2274 0.24638.7869 0.588 0 0.4643 0 0 0 14 11 16.189 11.8272 0.456 16.2648 0.0607 00 0 0.0929 0 14 12 20.3728 6.4137 0.5112 18.2357 0.1689 0 0 0 0 0 14 1316.2748 9.4744 0.5214 18.5997 0.0929 0 0 0 0 0 14 14 33.112 −4.85790.421 15.016 0.4029 0 0 0 0 0 14 15 29.8884 −3.2017 0.4765 16.99770.3685 0 0.4643 0 0 0 14 16 −2.8145 −3.2408 −0.0324 −1.1548 −0.0007 0 00 0 0 15 1 13.6193 8.337 0.4666 16.6454 0.0526 0 0 0.25 0.0714 0 15 213.5502 9.8693 0.5075 18.1036 0.0546 0 0 0.4375 0 0 15 3 10.6253 8.19110.3709 13.2302 0.0422 0 0 0.625 0 0 15 4 12.8991 9.5828 0.5149 18.36650.0614 0 0 0.8125 0 0 15 5 14.1788 10.2878 0.5371 19.1567 0.057 0 0.35711 0 0 15 6 15.9106 10.2565 0.5234 18.6704 0.0731 0 0 0 0.0714 0 15 725.1361 4.5535 0.5339 19.0451 0.246 0 0 0 0 0 15 8 17.3005 10.56530.5725 20.4196 0.0858 0 0 0 0 0 15 9 39.3304 −11.6055 0.3576 12.75430.5601 0 0 0 0 0 15 10 40.8823 −12.3612 0.3142 11.209 0.5896 0 0.3571 00 0 15 11 15.7257 8.0321 0.5488 19.5773 0.0844 0 0 0 0.714 0 15 1222.0656 1.9917 0.5208 18.5758 0.2347 0 0 0 0 0 15 13 22.8741 2.83640.4776 17.0345 0.2124 0 0 0 0 0 15 14 34.2248 −5.0631 0.374 13.34150.4307 0 0 0 0 0 15 15 33.8977 −5.8869 0.4112 14.666 0.4412 0 0.3571 0 00 15 16 −1.3407 −2.2066 0.0002 0.0063 −0.0076 0 0 0 0 0 16 1 3.70523.6884 0.2144 7.6482 0.0245 0 0 0.25 0.05 0 16 2 8.3106 4.9877 0.343212.2412 0.0346 0 0 0.4375 0 0 16 3 6.1593 3.1092 0.3153 11.2457 0.0373 00 0.625 0 0 16 4 7.5088 5.7052 0.3146 11.2232 0.0292 0 0 0.8125 0 0 16 511.8676 5.6885 0.4363 15.5639 0.0542 0 0.25 1 0 0 16 6 15.1336 5.64690.5604 19.9894 0.1525 0 0 0 0.05 0 16 7 27.5593 −2.1028 0.5175 18.45750.3154 0 0 0 0 0 16 8 23.5404 3.2796 0.5291 18.8719 0.2067 0 0 0 0 0 169 42.6335 −18.8531 0.2745 9.792 0.6582 0 0 0 0 0 16 10 44.5777 −22.16020.2137 7.6209 0.6973 0 0.25 0 0 0 16 11 19.465 3.5806 0.5718 20.39660.1768 0 0 0 0.05 0 16 12 31.6446 −9.6125 0.3109 11.0897 0.4374 0 0 0 00 16 13 29.2167 −9.3215 0.3039 10.8415 0.4154 0 0 0 0 0 16 14 28.5935−9.8595 0.2779 9.9111 0.4188 0 0 0 0 0 16 15 29.7075 −8.4891 0.293710.4778 0.4438 0 0.25 0 0 0 16 16 23.6652 4.1211 0.6603 23.552 0.20430.1275 0 0 0 0 R LaNO33 NH42TiOOX2 NH43SbOX3 PtNH32NO22 RhNO33 RuNONO33SnOX2 VOX2 ZrONO32 SUM_(—) real real real real real real real real realreal micromols Temperature: 300 C. 1 0 0 0 0 0 0 0 0 0 0.1275 1 0 0 0 00 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 00 0 0 1 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0.1275 1 0 0 0 0 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0.1275 0.04510 0 0 0 0.9583 11 0 0 0 0 0 0 0 0 0 0 12 0 0 0 0.1275 0 0 0 0 0 0.513212 0 0 0 0.1275 0 0 0.1357 0 0 0.7007 12 0 0 0.1357 0.1275 0 0 0 0 00.8882 12 0.6786 0 0 0.1275 0 0 0 0 0 1.6186 12 0 0 0 0.1275 0 0 0 0 01.8061 12 0 0 0 0.1275 0 0.056 0 0 0 0.3192 12 0 0 0 0.1275 0 0.0560.1357 0 0 0.3192 12 0 0 0.1357 0.1275 0 0.056 0 0 0 0.3192 12 0.6786 00 0.1275 0 0.056 0 0 0 0.8621 12 0 0 0 0.1275 0 0.056 0 0 0 0.8621 12 00 0 0.1275 0.0555 0 0 0 0 0.3188 12 0 0 0 0.1275 0.0555 0 0.1357 0 00.3188 12 0 0 0.1357 0.1275 0.0555 0 0 0 0 0.3188 12 0.6786 0 0 0.12750.0555 0 0 0 0 0.8616 12 0 0 0 0.1275 0.0555 0 0 0 0 0.8616 12 0 0 0 0 00 0 0 0 0 13 0 0 0 0.1275 0 0 0 0 0 0.4918 13 0 0 0 0.1275 0 0 0.1143 00 0.6793 13 0 0 0.1143 0.1275 0 0 0 0 0 0.8668 13 0.5714 0 0 0.1275 0 00 0 0 1.5114 13 0 0 0 0.1275 0 0 0 0 0 1.6989 13 0 0 0 0.1275 0 0.0665 00 0 0.3083 13 0 0 0 0.1275 0 0.0665 0.1143 0 0 0.3083 13 0 0 0.11430.1275 0 0.0665 0 0 0 0.3083 13 0.5714 0 0 0.1275 0 0.0665 0 0 0 0.765413 0 0 0 0.1275 0 0.0665 0 0 0 0.7654 13 0 0 0 0.1275 0.066 0 0 0 00.3077 13 0 0 0 0.1275 0.066 0 0.1143 0 0 0.3077 13 0 0 0.1143 0.12750.066 0 0 0 0 0.3077 13 0.5714 0 0 0.1275 0.066 0 0 0 0 0.7649 13 0 0 00.1275 0.066 0 0 0 0 0.7649 13 0 0 0 0 0 0 0 0 0 0.1275 14 0 0 0 0.12750 0 0 0 0 0.4704 14 0 0 0 0.1275 0 0 0.0929 0 0 0.6579 14 0 0 0.09290.1275 0 0 0 0 0 0.8454 14 0.4643 0 0 0.1275 0 0 0 0 0 1.4043 14 0 0 00.1275 0 0 0 0 0 1.5918 14 0 0 0 0.1275 0 0.077 0 0 0 0.2974 14 0 0 00.1275 0 0.077 0.0929 0 0 0.2974 14 0 0 0.0929 0.1275 0 0.077 0 0 00.2974 14 0.4643 0 0 0.1275 0 0.077 0 0 0 0.6688 14 0 0 0 0.1275 0 0.0770 0 0 0.6688 14 0 0 0 0.1275 0.0764 0 0 0 0 0.2967 14 0 0 0 0.12750.0764 0 0.0929 0 0 0.2967 14 0 0 0.0929 0.1275 0.0764 0 0 0 0 0.2967 140.4643 0 0 0.1275 0.0764 0 0 0 0 0.6682 14 0 0 0 0.1275 0.0764 0 0 0 00.6682 14 0 0 0 0 0 0 0 0 0 0 15 0 0 0 0.1275 0 0 0 0 0 0.4489 15 0 0 00.1275 0 0 0.0714 0 0 0.6364 15 0 0 0.0714 0.1275 0 0 0 0 0 0.8239 150.3571 0 0 0.1275 0 0 0 0 0 1.2971 15 0 0 0 0.1275 0 0 0 0 0 1.4846 15 00 0 0.1275 0 0.0875 0 0 0 0.2864 15 0 0 0 0.1275 0 0.0875 0.0714 0 00.2864 15 0 0 0.0714 0.1275 0 0.0875 0 0 0 0.2864 15 0.3571 0 0 0.1275 00.0875 0 0 0 0.5721 15 0 0 0 0.1275 0 0.0875 0 0 0 0.5721 15 0 0 00.1275 0.0868 0 0 0 0 0.2857 15 0 0 0 0.1275 0.0868 0 0.0714 0 0 0.285715 0 0 0.0714 0.1275 0.0868 0 0 0 0 0.2857 15 0.3571 0 0 0.1275 0.0868 00 0 0 0.5714 15 0 0 0 0.1275 0.0868 0 0 0 0 0.5714 15 0 0 0 0 0 0 0 0 00 16 0 0 0 0.1275 0 0 0 0 0 0.4275 16 0 0 0 0.1275 0 0 0.05 0 0 0.615 160 0 0.05 0.1275 0 0 0 0 0 0.8025 16 0.25 0 0 0.1275 0 0 0 0 0 1.19 16 00 0 0.1275 0 0 0 0 0 1.3775 16 0 0 0 0.1275 0 0.098 0 0 0 0.2755 16 0 00 0.1275 0 0.098 0.05 0 0 0.2755 16 0 0 0.05 0.1275 0 0.098 0 0 0 0.275516 0.25 0 0 0.1275 0 0.098 0 0 0 0.4755 16 0 0 0 0.1275 0 0.098 0 0 00.4755 16 0 0 0 0.1275 0.0972 0 0 0 0 0.2747 16 0 0 0 0.1275 0.0972 00.05 0 0 0.2747 16 0 0 0.05 0.1275 0.0972 0 0 0 0 0.2747 16 0.25 0 00.1275 0.0972 0 0 0 0 0.4747 16 0 0 0 0.1275 0.0972 0 0 0 0 0.4747 16 00 0 0 0 0 0 0 0 0.1275 R mol % mol % mol % mol % mol % mol % mol % mol %mol % mol % mol % mol % mol % real Co Fe Ge Mo La Ti Sb Pt Rh Ru Sn V ZrTemperature: 300 C. 1 0 0 0 0 0 0 0 100 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 00 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 00 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 100 0 0 00 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 00 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 01 0 0 0 0 0 0 0 100 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 00 0 0 0 0 0 0 1 0 0 0 0 0 0 0 100 0 0 0 0 0 2 0 47 0 0 0 47 0 5.99 0 0 00 0 2 0 47 0 0 0 0 0 5.99 0 0 0 0 47 2 0 47 0 0 0 0 0 5.99 0 0 0 47 0 20 47 0 47 0 0 0 5.99 0 0 0 0 0 2 47 47 0 0 0 0 0 5.99 0 0 0 0 0 2 0 0 00 0 86.81 0 11.07 0 2.13 0 0 0 2 0 0 0 0 0 0 0 11.07 0 2.13 0 0 86.81 20 0 0 0 0 0 0 11.07 0 2.13 0 86.81 0 2 0 0 0 86.81 0 0 0 11.07 0 2.13 00 0 2 86.81 0 0 0 0 0 0 11.07 0 2.13 0 0 0 2 0 0 0 0 0 86.82 0 11.072.11 0 0 0 0 2 0 0 0 0 0 0 0 11.07 2.11 0 0 0 86.82 2 0 0 0 0 0 0 011.07 2.11 0 0 86.82 0 2 0 0 0 86.82 0 0 0 11.07 2.11 0 0 0 0 2 86.82 00 0 0 0 0 11.07 2.11 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0 46.6 0 0 046.6 0 6.79 0 0 0 0 0 3 0 46.6 0 0 0 0 0 6.79 0 0 0 0 46.6 3 0 46.6 0 00 0 0 6.79 0 0 0 46.6 0 3 0 46.6 0 46.6 0 0 0 6.79 0 0 0 0 0 3 46.6 46.60 0 0 0 0 6.79 0 0 0 0 0 3 0 0 0 0 0 84.2 0 12.27 0 3.54 0 0 0 3 0 0 0 00 0 0 12.27 0 3.54 0 0 84.2 3 0 0 0 0 0 0 0 12.27 0 3.54 0 84.2 0 3 0 00 84.2 0 0 0 12.27 0 3.54 0 0 0 3 84.2 0 0 0 0 0 0 12.27 0 3.54 0 0 0 30 0 0 0 0 84.22 0 12.27 3.51 0 0 0 0 3 0 0 0 0 0 0 0 12.27 3.51 0 0 084.22 3 0 0 0 0 0 0 0 12.27 3.51 0 0 84.22 0 3 0 0 0 84.22 0 0 0 12.273.51 0 0 0 0 3 84.22 0 0 0 0 0 0 12.27 3.51 0 0 0 0 3 0 0 0 0 0 0 0 0 00 0 0 0 4 0 46.08 0 0 0 46.08 0 7.83 0 0 0 0 0 4 0 46.08 0 0 0 0 0 7.830 0 0 0 46.08 4 0 46.08 0 0 0 0 0 7.83 0 0 0 46.08 0 4 0 46.08 0 46.08 00 0 7.83 0 0 0 0 0 4 46.08 46.08 0 0 0 0 0 7.83 0 0 0 0 0 4 0 0 0 0 080.95 0 13.76 0 5.29 0 0 0 4 0 0 0 0 0 0 0 13.76 0 5.29 0 0 80.95 4 0 00 0 0 0 0 13.76 0 5.29 0 80.95 0 4 0 0 0 80.95 0 0 0 13.76 0 5.29 0 0 04 80.95 0 0 0 0 0 0 13.76 0 5.29 0 0 0 4 0 0 0 0 0 80.98 0 13.77 5.25 00 0 0 4 0 0 0 0 0 0 0 13.77 5.25 0 0 0 80.98 4 0 0 0 0 0 0 0 13.77 5.250 0 80.98 0 4 0 0 0 80.98 0 0 0 13.77 5.25 0 0 0 0 4 80.98 0 0 0 0 0 013.77 5.25 0 0 0 0 4 0 0 0 0 0 0 0 100 0 0 0 0 0 5 0 45.37 0 0 0 45.37 09.26 0 0 0 0 0 5 0 45.37 0 0 0 0 0 9.26 0 0 0 0 45.37 5 0 45.37 0 0 0 00 9.26 0 0 0 45.37 0 5 0 45.37 0 45.37 0 0 0 9.26 0 0 0 0 0 5 45.3745.37 0 0 0 0 0 9.26 0 0 0 0 0 5 0 0 0 0 0 76.8 0 15.67 0 7.53 0 0 0 5 00 0 0 0 0 0 15.67 0 7.53 0 0 76.8 5 0 0 0 0 0 0 0 15.67 0 7.53 0 76.8 05 0 0 0 76.8 0 0 0 15.67 0 7.53 0 0 0 5 76.8 0 0 0 0 0 0 15.67 0 7.53 00 0 5 0 0 0 0 0 76.85 0 15.68 7.47 0 0 0 0 5 0 0 0 0 0 0 0 15.68 7.47 00 0 76.85 5 0 0 0 0 0 0 0 15.68 7.47 0 0 76.85 0 5 0 0 0 76.85 0 0 015.68 7.47 0 0 0 0 5 76.85 0 0 0 0 0 0 15.68 7.47 0 0 0 0 5 0 0 0 0 0 00 0 0 0 0 0 0 6 0 44.35 0 0 0 44.35 0 11.31 0 0 0 0 0 6 0 44.35 0 0 0 00 11.31 0 0 0 0 44.35 6 0 44.35 0 0 0 0 0 11.31 0 0 0 44.35 0 6 0 44.350 44.35 0 0 0 11.31 0 0 0 0 0 6 44.35 44.35 0 0 0 0 0 11.31 0 0 0 0 0 60 0 0 0 0 71.33 0 18.19 0 10.49 0 0 0 6 0 0 0 0 0 0 0 18.19 0 10.49 0 071.33 6 0 0 0 0 0 0 0 18.19 0 10.49 0 71.33 0 6 0 0 0 71.33 0 0 0 18.190 10.49 0 0 0 6 71.33 0 0 0 0 0 0 18.19 0 10.49 0 0 0 6 0 0 0 0 0 71.390 18.2 10.41 0 0 0 0 6 0 0 0 0 0 0 0 18.2 10.41 0 0 0 71.39 6 0 0 0 0 00 0 18.2 10.41 0 0 71.39 0 6 0 0 0 71.39 0 0 0 18.2 10.41 0 0 0 0 671.39 0 0 0 0 0 0 18.2 10.41 0 0 0 0 6 0 0 0 0 0 0 0 0 0 0 0 0 0 7 042.74 0 0 0 42.74 0 14.53 0 0 0 0 0 7 0 42.74 0 0 0 0 0 14.53 0 0 0 042.74 7 0 42.74 0 0 0 0 0 14.53 0 0 0 42.74 0 7 0 42.74 0 42.74 0 0 014.53 0 0 0 0 0 7 42.74 42.74 0 0 0 0 0 14.53 0 0 0 0 0 7 0 0 0 0 063.75 0 21.67 0 14.58 0 0 0 7 0 0 0 0 0 0 0 21.67 0 14.58 0 0 63.75 7 00 0 0 0 0 0 21.67 0 14.58 0 63.75 0 7 0 0 0 63.75 0 0 0 21.67 0 14.58 00 0 7 63.75 0 0 0 0 0 0 21.67 0 14.58 0 0 0 7 0 0 0 0 0 63.82 0 21.714.48 0 0 0 0 7 0 0 0 0 0 0 0 21.7 14.48 0 0 0 63.82 7 0 0 0 0 0 0 021.7 14.48 0 0 63.82 0 7 0 0 0 63.82 0 0 0 21.7 14.48 0 0 0 0 7 63.82 00 0 0 0 0 21.7 14.48 0 0 0 0 7 0 0 0 0 0 0 0 100 0 0 0 0 0 8 0 39.84 0 00 39.84 0 20.32 0 0 0 0 0 8 0 39.84 0 0 0 0 0 20.32 0 0 0 0 39.84 8 039.84 0 0 0 0 0 20.32 0 0 0 39.84 0 8 0 39.84 0 39.84 0 0 0 20.32 0 0 00 0 8 39.84 39.84 0 0 0 0 0 20.32 0 0 0 0 0 8 0 0 0 0 0 52.58 0 26.81 020.61 0 0 0 8 0 0 0 0 0 0 0 26.81 0 20.61 0 0 52.58 8 0 0 0 0 0 0 026.81 0 20.61 0 52.58 0 8 0 0 0 52.58 0 0 0 26.81 0 20.61 0 0 0 8 52.580 0 0 0 0 0 26.81 0 20.61 0 0 0 8 0 0 0 0 0 52.66 0 26.86 20.48 0 0 0 08 0 0 0 0 0 0 0 26.86 20.48 0 0 0 52.66 8 0 0 0 0 0 0 0 26.86 20.48 0 052.66 0 8 0 0 0 52.66 0 0 0 26.86 20.48 0 0 0 0 8 52.66 0 0 0 0 0 026.86 20.48 0 0 0 0 8 0 0 0 0 0 0 0 0 0 0 0 0 0 9 0 43.29 34.63 0 0 0 022.08 0 0 0 0 0 9 0 57.19 0 0 0 0 0 16.67 0 0 26.14 0 0 9 0 65.62 0 0 00 21 13.39 0 0 0 0 0 9 0 41.88 0 0 51.55 0 0 6.57 0 0 0 0 0 9 47 47 0 00 0 0 5.99 0 0 0 0 0 9 0 0 56.82 0 0 0 0 36.22 0 6.96 0 0 0 9 0 0 0 0 00 0 36.22 0 6.96 56.82 0 0 9 0 0 0 0 0 0 56.82 36.22 0 6.96 0 0 0 9 0 00 0 86.81 0 0 11.07 0 2.13 0 0 0 9 86.81 0 0 0 0 0 0 11.07 0 2.13 0 0 09 0 0 56.85 0 0 0 0 36.24 6.91 0 0 0 0 9 0 0 0 0 0 0 0 36.24 6.91 056.85 0 0 9 0 0 0 0 0 0 56.85 36.24 6.91 0 0 0 0 9 0 0 0 0 86.82 0 011.07 2.11 0 0 0 0 9 86.82 0 0 0 0 0 0 11.07 2.11 0 0 0 0 9 0 0 0 0 0 00 0 0 0 0 0 0 10 0 44.96 32.11 0 0 0 0 22.93 0 0 0 0 0 10 0 58.84 0 0 00 0 17.15 0 0 24.02 0 0 10 0 67.13 0 0 0 0 19.18 13.69 0 0 0 0 0 10 044.33 0 0 48.71 0 0 6.96 0 0 0 0 0 10 44.19 49.5 0 0 0 0 0 6.31 0 0 0 00 10 0 0 52.36 0 0 0 0 37.38 0 10.26 0 0 0 10 0 0 0 0 0 0 0 37.38 010.26 52.36 0 0 10 0 0 0 0 0 0 52.36 37.38 0 10.26 0 0 0 10 0 0 0 0 84.60 0 12.08 0 3.32 0 0 0 10 84.6 0 0 0 0 0 0 12.08 0 3.32 0 0 0 10 0 052.4 0 0 0 0 37.41 10.19 0 0 0 0 10 0 0 0 0 0 0 0 37.41 10.19 0 52.4 0 010 0 0 0 0 0 0 52.4 37.41 10.19 0 0 0 0 10 0 0 0 0 84.63 0 0 12.08 3.290 0 0 0 10 84.63 0 0 0 0 0 0 12.08 3.29 0 0 0 0 10 0 0 0 0 0 0 0 100 0 00 0 0 11 0 46.76 29.39 0 0 0 0 23.85 0 0 0 0 0 11 0 60.58 0 0 0 0 017.66 0 0 21.76 0 0 11 0 68.71 0 0 0 0 17.28 14.02 0 0 0 0 0 11 0 47.080 0 45.53 0 0 7.39 0 0 0 0 0 11 41.07 52.27 0 0 0 0 0 6.66 0 0 0 0 0 110 0 47.6 0 0 0 0 38.62 0 13.78 0 0 0 11 0 0 0 0 0 0 0 38.62 0 13.78 47.60 0 11 0 0 0 0 0 0 47.6 38.62 0 13.78 0 0 0 11 0 0 0 0 81.95 0 0 13.3 04.75 0 0 0 11 81.95 0 0 0 0 0 0 13.3 0 4.75 0 0 0 11 0 0 47.65 0 0 0 038.66 13.68 0 0 0 0 11 0 0 0 0 0 0 0 38.66 13.68 0 47.65 0 0 11 0 0 0 00 0 47.65 38.66 13.68 0 0 0 0 11 0 0 0 0 81.99 0 0 13.3 4.71 0 0 0 0 1181.99 0 0 0 0 0 0 13.3 4.71 0 0 0 0 11 0 0 0 0 0 0 0 0 0 0 0 0 0 12 048.71 26.44 0 0 0 0 24.84 0 0 0 0 0 12 0 62.44 0 0 0 0 0 18.2 0 0 19.370 0 12 0 70.37 0 0 0 0 15.28 14.35 0 0 0 0 0 12 0 50.2 0 0 41.92 0 07.88 0 0 0 0 0 12 37.57 55.37 0 0 0 0 0 7.06 0 0 0 0 0 12 0 0 42.52 0 00 0 39.94 0 17.54 0 0 0 12 0 0 0 0 0 0 0 39.94 0 17.54 42.52 0 0 12 0 00 0 0 0 42.52 39.94 0 17.54 0 0 0 12 0 0 0 0 78.71 0 0 14.79 0 6.5 0 0 012 78.71 0 0 0 0 0 0 14.79 0 6.5 0 0 0 12 0 0 42.58 0 0 0 0 40 17.42 0 00 0 12 0 0 0 0 0 0 0 40 17.42 0 42.58 0 0 12 0 0 0 0 0 0 42.58 40 17.420 0 0 0 12 0 0 0 0 78.76 0 0 14.8 6.45 0 0 0 0 12 78.76 0 0 0 0 0 0 14.86.45 0 0 0 0 12 0 0 0 0 0 0 0 0 0 0 0 0 0 13 0 50.84 23.24 0 0 0 0 25.930 0 0 0 0 13 0 64.41 0 0 0 0 0 18.77 0 0 16.82 0 0 13 0 72.11 0 0 0 013.19 14.71 0 0 0 0 0 13 0 53.76 0 0 37.81 0 0 8.44 0 0 0 0 0 13 33.6358.86 0 0 0 0 0 7.5 0 0 0 0 0 13 0 0 37.07 0 0 0 0 41.36 0 21.57 0 0 013 0 0 0 0 0 0 0 41.36 0 21.57 37.07 0 0 13 0 0 0 0 0 0 37.07 41.36 021.57 0 0 0 13 0 0 0 0 74.65 0 0 16.66 0 8.69 0 0 0 13 74.65 0 0 0 0 0 016.66 0 8.69 0 0 0 13 0 0 37.14 0 0 0 0 41.43 21.43 0 0 0 0 13 0 0 0 0 00 0 41.43 21.43 0 37.14 0 0 13 0 0 0 0 0 0 37.14 41.43 21.43 0 0 0 0 130 0 0 0 74.71 0 0 16.67 8.62 0 0 0 0 13 74.71 0 0 0 0 0 0 16.67 8.62 0 00 0 13 0 0 0 0 0 0 0 100 0 0 0 0 0 14 0 53.15 19.74 0 0 0 0 27.11 0 0 00 0 14 0 66.5 0 0 0 0 0 19.38 0 0 14.12 0 0 14 0 73.93 0 0 0 0 10.9815.08 0 0 0 0 0 14 0 57.86 0 0 33.06 0 0 9.08 0 0 0 0 0 14 29.17 62.82 00 0 0 0 8.01 0 0 0 0 0 14 0 0 31.23 0 0 0 0 42.88 0 25.89 0 0 0 14 0 0 00 0 0 0 42.88 0 25.89 31.23 0 0 14 0 0 0 0 0 0 31.23 42.88 0 25.89 0 0 014 0 0 0 0 69.42 0 0 19.06 0 11.51 0 0 0 14 69.42 0 0 0 0 0 0 19.06 011.51 0 0 0 14 0 0 31.29 0 0 0 0 42.97 25.74 0 0 0 0 14 0 0 0 0 0 0 042.97 25.74 0 31.29 0 0 14 0 0 0 0 0 0 31.29 42.97 25.74 0 0 0 0 14 0 00 0 69.49 0 0 19.08 11.43 0 0 0 0 14 69.49 0 0 0 0 0 0 19.08 11.43 0 0 00 14 0 0 0 0 0 0 0 0 0 0 0 0 0 15 0 55.69 15.91 0 0 0 0 28.4 0 0 0 0 015 0 68.74 0 0 0 0 0 20.03 0 0 11.22 0 0 15 0 75.86 0 0 0 0 8.67 15.47 00 0 0 0 15 0 62.64 0 0 27.53 0 0 9.83 0 0 0 0 0 15 24.06 67.36 0 0 0 0 08.59 0 0 0 0 0 15 0 0 24.94 0 0 0 0 44.51 0 30.55 0 0 0 15 0 0 0 0 0 0 044.51 0 30.55 24.94 0 0 15 0 0 0 0 0 0 24.94 44.51 0 30.55 0 0 0 15 0 00 0 62.42 0 0 22.28 0 15.29 0 0 0 15 62.42 0 0 0 0 0 0 22.28 0 15.29 0 00 15 0 0 25 0 0 0 0 44.63 30.37 0 0 0 0 15 0 0 0 0 0 0 0 44.63 30.37 025 0 0 15 0 0 0 0 0 0 25 44.63 30.37 0 0 0 0 15 0 0 0 0 62.5 0 0 22.3115.19 0 0 0 0 15 62.5 0 0 0 0 0 0 22.31 15.19 0 0 0 0 15 0 0 0 0 0 0 0 00 0 0 0 0 16 0 58.48 11.7 0 0 0 0 29.82 0 0 0 0 0 16 0 71.14 0 0 0 0 020.73 0 0 8.13 0 0 16 0 77.88 0 0 0 0 6.23 15.89 0 0 0 0 0 16 0 68.28 00 21.01 0 0 10.71 0 0 0 0 0 16 18.15 72.6 0 0 0 0 0 9.26 0 0 0 0 0 16 00 18.15 0 0 0 0 46.28 0 35.57 0 0 0 16 0 0 0 0 0 0 0 46.28 0 35.57 18.150 0 16 0 0 0 0 0 0 18.15 46.28 0 35.57 0 0 0 16 0 0 0 0 52.58 0 0 26.810 20.61 0 0 0 16 52.58 0 0 0 0 0 0 26.81 0 20.61 0 0 0 16 0 0 18.2 0 0 00 46.41 35.38 0 0 0 0 16 0 0 0 0 0 0 0 46.41 35.38 0 18.2 0 0 16 0 0 0 00 0 18.2 46.41 35.38 0 0 0 0 16 0 0 0 0 52.66 0 0 26.86 20.48 0 0 0 0 1652.66 0 0 0 0 0 0 26.86 20.48 0 0 0 0 16 0 0 0 0 0 0 0 100 0 0 0 0 0Temperature: 350 C. 1 0 0 0 0 0 0 0 100 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 00 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 00 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 100 0 0 00 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 00 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 01 0 0 0 0 0 0 0 100 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 00 0 0 0 0 0 0 1 0 0 0 0 0 0 0 100 0 0 0 0 0 2 0 47 0 0 0 47 0 5.99 0 0 00 0 2 0 47 0 0 0 0 0 5.99 0 0 0 0 47 2 0 47 0 0 0 0 0 5.99 0 0 0 47 0 20 47 0 47 0 0 0 5.99 0 0 0 0 0 2 47 47 0 0 0 0 0 5.99 0 0 0 0 0 2 0 0 00 0 86.81 0 11.07 0 2.13 0 0 0 2 0 0 0 0 0 0 0 11.07 0 2.13 0 0 86.81 20 0 0 0 0 0 0 11.07 0 2.13 0 86.81 0 2 0 0 0 86.81 0 0 0 11.07 0 2.13 00 0 2 86.81 0 0 0 0 0 0 11.07 0 2.13 0 0 0 2 0 0 0 0 0 86.82 0 11.072.11 0 0 0 0 2 0 0 0 0 0 0 0 11.07 2.11 0 0 0 86.82 2 0 0 0 0 0 0 011.07 2.11 0 0 86.82 0 2 0 0 0 86.82 0 0 0 11.07 2.11 0 0 0 0 2 86.82 00 0 0 0 0 11.07 2.11 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0 46.6 0 0 046.6 0 6.79 0 0 0 0 0 3 0 46.6 0 0 0 0 0 6.79 0 0 0 0 46.6 3 0 46.6 0 00 0 0 6.79 0 0 0 46.6 0 3 0 46.6 0 46.6 0 0 0 6.79 0 0 0 0 0 3 46.6 46.60 0 0 0 0 6.79 0 0 0 0 0 3 0 0 0 0 0 84.2 0 12.27 0 3.54 0 0 0 3 0 0 0 00 0 0 12.27 0 3.54 0 0 84.2 3 0 0 0 0 0 0 0 12.27 0 3.54 0 84.2 0 3 0 00 84.2 0 0 0 12.27 0 3.54 0 0 0 3 84.2 0 0 0 0 0 0 12.27 0 3.54 0 0 0 30 0 0 0 0 84.22 0 12.27 3.51 0 0 0 0 3 0 0 0 0 0 0 0 12.27 3.51 0 0 084.22 3 0 0 0 0 0 0 0 12.27 3.51 0 0 84.22 0 3 0 0 0 84.22 0 0 0 12.273.51 0 0 0 0 3 84.22 0 0 0 0 0 0 12.27 3.51 0 0 0 0 3 0 0 0 0 0 0 0 0 00 0 0 0 4 0 46.08 0 0 0 46.08 0 7.83 0 0 0 0 0 4 0 46.08 0 0 0 0 0 7.830 0 0 0 46.08 4 0 46.08 0 0 0 0 0 7.83 0 0 0 46.08 0 4 0 46.08 0 46.08 00 0 7.83 0 0 0 0 0 4 46.08 46.08 0 0 0 0 0 7.83 0 0 0 0 0 4 0 0 0 0 080.95 0 13.76 0 5.29 0 0 0 4 0 0 0 0 0 0 0 13.76 0 5.29 0 0 80.95 4 0 00 0 0 0 0 13.76 0 5.29 0 80.95 0 4 0 0 0 80.95 0 0 0 13.76 0 5.29 0 0 04 80.95 0 0 0 0 0 0 13.76 0 5.29 0 0 0 4 0 0 0 0 0 80.98 0 13.77 5.25 00 0 0 4 0 0 0 0 0 0 0 13.77 5.25 0 0 0 80.98 4 0 0 0 0 0 0 0 13.77 5.250 0 80.98 0 4 0 0 0 80.98 0 0 0 13.77 5.25 0 0 0 0 4 80.98 0 0 0 0 0 013.77 5.25 0 0 0 0 4 0 0 0 0 0 0 0 100 0 0 0 0 0 5 0 45.37 0 0 0 45.37 09.26 0 0 0 0 0 5 0 45.37 0 0 0 0 0 9.26 0 0 0 0 45.37 5 0 45.37 0 0 0 00 9.26 0 0 0 45.37 0 5 0 45.37 0 45.37 0 0 0 9.26 0 0 0 0 0 5 45.3745.37 0 0 0 0 0 9.26 0 0 0 0 0 5 0 0 0 0 0 76.8 0 15.67 0 7.53 0 0 0 5 00 0 0 0 0 0 15.67 0 7.53 0 0 76.8 5 0 0 0 0 0 0 0 15.67 0 7.53 0 76.8 05 0 0 0 76.8 0 0 0 15.67 0 7.53 0 0 0 5 76.8 0 0 0 0 0 0 15.67 0 7.53 00 0 5 0 0 0 0 0 76.85 0 15.68 7.47 0 0 0 0 5 0 0 0 0 0 0 0 15.68 7.47 00 0 76.85 5 0 0 0 0 0 0 0 15.68 7.47 0 0 76.85 0 5 0 0 0 76.85 0 0 015.68 7.47 0 0 0 0 5 76.85 0 0 0 0 0 0 15.68 7.47 0 0 0 0 5 0 0 0 0 0 00 0 0 0 0 0 0 6 0 44.35 0 0 0 44.35 0 11.31 0 0 0 0 0 6 0 44.35 0 0 0 00 11.31 0 0 0 0 44.35 6 0 44.35 0 0 0 0 0 11.31 0 0 0 44.35 0 6 0 44.350 44.35 0 0 0 11.31 0 0 0 0 0 6 44.35 44.35 0 0 0 0 0 11.31 0 0 0 0 0 60 0 0 0 0 71.33 0 18.19 0 10.49 0 0 0 6 0 0 0 0 0 0 0 18.19 0 10.49 0 071.33 6 0 0 0 0 0 0 0 18.19 0 10.49 0 71.33 0 6 0 0 0 71.33 0 0 0 18.190 10.49 0 0 0 6 71.33 0 0 0 0 0 0 18.19 0 10.49 0 0 0 6 0 0 0 0 0 71.390 18.2 10.41 0 0 0 0 6 0 0 0 0 0 0 0 18.2 10.41 0 0 0 71.39 6 0 0 0 0 00 0 18.2 10.41 0 0 71.39 0 6 0 0 0 71.39 0 0 0 18.2 10.41 0 0 0 0 671.39 0 0 0 0 0 0 18.2 10.41 0 0 0 0 6 0 0 0 0 0 0 0 0 0 0 0 0 0 7 042.74 0 0 0 42.74 0 14.53 0 0 0 0 0 7 0 42.74 0 0 0 0 0 14.53 0 0 0 042.74 7 0 42.74 0 0 0 0 0 14.53 0 0 0 42.74 0 7 0 42.74 0 42.74 0 0 014.53 0 0 0 0 0 7 42.74 42.74 0 0 0 0 0 14.53 0 0 0 0 0 7 0 0 0 0 063.75 0 21.67 0 14.58 0 0 0 7 0 0 0 0 0 0 0 21.67 0 14.58 0 0 63.75 7 00 0 0 0 0 0 21.67 0 14.58 0 63.75 0 7 0 0 0 63.75 0 0 0 21.67 0 14.58 00 0 7 63.75 0 0 0 0 0 0 21.67 0 14.58 0 0 0 7 0 0 0 0 0 63.82 0 21.714.48 0 0 0 0 7 0 0 0 0 0 0 0 21.7 14.48 0 0 0 63.82 7 0 0 0 0 0 0 021.7 14.48 0 0 63.82 0 7 0 0 0 63.82 0 0 0 21.7 14.48 0 0 0 0 7 63.82 00 0 0 0 0 21.7 14.48 0 0 0 0 7 0 0 0 0 0 0 0 100 0 0 0 0 0 8 0 39.84 0 00 39.84 0 20.32 0 0 0 0 0 8 0 39.84 0 0 0 0 0 20.32 0 0 0 0 39.84 8 039.84 0 0 0 0 0 20.32 0 0 0 39.84 0 8 0 39.84 0 39.84 0 0 0 20.32 0 0 00 0 8 39.84 39.84 0 0 0 0 0 20.32 0 0 0 0 0 8 0 0 0 0 0 52.58 0 26.81 020.61 0 0 0 8 0 0 0 0 0 0 0 26.81 0 20.61 0 0 52.58 8 0 0 0 0 0 0 026.81 0 20.61 0 52.58 0 8 0 0 0 52.58 0 0 0 26.81 0 20.61 0 0 0 8 52.580 0 0 0 0 0 26.81 0 20.61 0 0 0 8 0 0 0 0 0 52.66 0 26.86 20.48 0 0 0 08 0 0 0 0 0 0 0 26.86 20.48 0 0 0 52.66 8 0 0 0 0 0 0 0 26.86 20.48 0 052.66 0 8 0 0 0 52.66 0 0 0 26.86 20.48 0 0 0 0 8 52.66 0 0 0 0 0 026.86 20.48 0 0 0 0 8 0 0 0 0 0 0 0 0 0 0 0 0 0 9 0 43.29 34.63 0 0 0 022.08 0 0 0 0 0 9 0 57.19 0 0 0 0 0 16.67 0 0 26.14 0 0 9 0 65.62 0 0 00 21 13.39 0 0 0 0 0 9 0 41.88 0 0 51.55 0 0 6.57 0 0 0 0 0 9 47 47 0 00 0 0 5.99 0 0 0 0 0 9 0 0 56.82 0 0 0 0 36.22 0 6.96 0 0 0 9 0 0 0 0 00 0 36.22 0 6.96 56.82 0 0 9 0 0 0 0 0 0 56.82 36.22 0 6.96 0 0 0 9 0 00 0 86.81 0 0 11.07 0 2.13 0 0 0 9 86.81 0 0 0 0 0 0 11.07 0 2.13 0 0 09 0 0 56.85 0 0 0 0 36.24 6.91 0 0 0 0 9 0 0 0 0 0 0 0 36.24 6.91 056.85 0 0 9 0 0 0 0 0 0 56.85 36.24 6.91 0 0 0 0 9 0 0 0 0 86.82 0 011.07 2.11 0 0 0 0 9 86.82 0 0 0 0 0 0 11.07 2.11 0 0 0 0 9 0 0 0 0 0 00 0 0 0 0 0 0 10 0 44.96 32.11 0 0 0 0 22.93 0 0 0 0 0 10 0 58.84 0 0 00 0 17.15 0 0 24.01 0 0 536998 10 0 67.13 0 0 0 0 19.18 13.69 0 0 0 0 010 0 44.33 0 0 48.71 0 0 6.96 0 0 0 0 0 10 44.19 49.5 0 0 0 0 0 6.31 0 00 0 0 10 0 0 52.36 0 0 0 0 37.38 0 10.26 0 0 0 10 0 0 0 0 0 0 0 37.38 010.26 52.36 0 0 10 0 0 0 0 0 0 52.36 37.38 0 10.26 0 0 0 10 0 0 0 0 84.60 0 12.08 0 3.32 0 0 0 10 84.6 0 0 0 0 0 0 12.08 0 3.32 0 0 0 10 0 052.4 0 0 0 0 37.41 10.19 0 0 0 0 10 0 0 0 0 0 0 0 37.41 10.19 0 52.4 0 010 0 0 0 0 0 0 52.4 37.41 10.19 0 0 0 0 10 0 0 0 0 84.63 0 0 12.08 3.290 0 0 0 10 84.63 0 0 0 0 0 0 12.08 3.29 0 0 0 0 10 0 0 0 0 0 0 0 100 0 00 0 0 11 0 46.76 29.39 0 0 0 0 23.85 0 0 0 0 0 11 0 60.58 0 0 0 0 017.66 0 0 21.76 0 0 11 0 68.71 0 0 0 0 17.28 14.02 0 0 0 0 0 11 0 47.080 0 45.53 0 0 7.39 0 0 0 0 0 11 41.07 52.27 0 0 0 0 0 6.66 0 0 0 0 0 110 0 47.6 0 0 0 0 38.62 0 13.78 0 0 0 11 0 0 0 0 0 0 0 38.62 0 13.78 47.60 0 11 0 0 0 0 0 0 47.6 38.62 0 13.78 0 0 0 11 0 0 0 0 81.95 0 0 13.3 04.75 0 0 0 11 81.95 0 0 0 0 0 0 13.3 0 4.75 0 0 0 11 0 0 47.65 0 0 0 038.66 13.68 0 0 0 0 11 0 0 0 0 0 0 0 38.66 13.68 0 47.65 0 0 11 0 0 0 00 0 47.65 38.66 13.68 0 0 0 0 11 0 0 0 0 81.99 0 0 13.3 4.71 0 0 0 0 1181.99 0 0 0 0 0 0 13.3 4.71 0 0 0 0 11 0 0 0 0 0 0 0 0 0 0 0 0 0 12 048.71 26.44 0 0 0 0 24.84 0 0 0 0 0 12 0 62.44 0 0 0 0 0 18.2 0 0 19.370 0 12 0 70.37 0 0 0 0 15.28 14.35 0 0 0 0 0 12 0 50.2 0 0 41.92 0 07.88 0 0 0 0 0 12 37.57 55.37 0 0 0 0 0 7.06 0 0 0 0 0 12 0 0 42.52 0 00 0 39.94 0 17.54 0 0 0 12 0 0 0 0 0 0 0 39.94 0 17.54 42.52 0 0 12 0 00 0 0 0 42.52 39.94 0 17.54 0 0 0 12 0 0 0 0 78.71 0 0 14.79 0 6.5 0 0 012 78.71 0 0 0 0 0 0 14.79 0 6.5 0 0 0 12 0 0 42.58 0 0 0 0 40 17.42 0 00 0 12 0 0 0 0 0 0 0 40 17.42 0 42.58 0 0 12 0 0 0 0 0 0 42.58 40 17.420 0 0 0 12 0 0 0 0 78.76 0 0 14.8 6.45 0 0 0 0 12 78.76 0 0 0 0 0 0 14.86.45 0 0 0 0 12 0 0 0 0 0 0 0 0 0 0 0 0 0 13 0 50.84 23.24 0 0 0 0 25.930 0 0 0 0 13 0 64.41 0 0 0 0 0 18.77 0 0 16.82 0 0 13 0 72.11 0 0 0 013.19 14.71 0 0 0 0 0 13 0 53.76 0 0 37.81 0 0 8.44 0 0 0 0 0 13 33.6358.86 0 0 0 0 0 7.5 0 0 0 0 0 13 0 0 37.07 0 0 0 0 41.36 0 21.57 0 0 013 0 0 0 0 0 0 0 41.36 0 21.57 37.07 0 0 13 0 0 0 0 0 0 37.07 41.36 021.57 0 0 0 13 0 0 0 0 74.65 0 0 16.66 0 8.69 0 0 0 13 74.65 0 0 0 0 0 016.66 0 8.69 0 0 0 13 0 0 37.14 0 0 0 0 41.43 21.43 0 0 0 0 13 0 0 0 0 00 0 41.43 21.43 0 37.14 0 0 13 0 0 0 0 0 0 37.14 41.43 21.43 0 0 0 0 130 0 0 0 74.71 0 0 16.67 8.62 0 0 0 0 13 74.71 0 0 0 0 0 0 16.67 8.62 0 00 0 13 0 0 0 0 0 0 0 100 0 0 0 0 0 14 0 53.15 19.74 0 0 0 0 27.11 0 0 00 0 14 0 66.5 0 0 0 0 0 19.38 0 0 14.12 0 0 14 0 73.93 0 0 0 0 10.9815.08 0 0 0 0 0 14 0 57.86 0 0 33.06 0 0 9.08 0 0 0 0 0 14 29.17 62.82 00 0 0 0 8.01 0 0 0 0 0 14 0 0 31.23 0 0 0 0 42.88 0 25.89 0 0 0 14 0 0 00 0 0 0 42.88 0 25.89 31.23 0 0 14 0 0 0 0 0 0 31.23 42.88 0 25.89 0 0 014 0 0 0 0 69.42 0 0 19.06 0 11.51 0 0 0 14 69.42 0 0 0 0 0 0 19.06 011.51 0 0 0 14 0 0 31.29 0 0 0 0 42.97 25.74 0 0 0 0 14 0 0 0 0 0 0 042.97 25.74 0 31.29 0 0 14 0 0 0 0 0 0 31.29 42.97 25.74 0 0 0 0 14 0 00 0 69.49 0 0 19.08 11.43 0 0 0 0 14 69.49 0 0 0 0 0 0 19.08 11.43 0 0 00 14 0 0 0 0 0 0 0 0 0 0 0 0 0 15 0 55.69 15.91 0 0 0 0 28.4 0 0 0 0 015 0 68.74 0 0 0 0 0 20.03 0 0 11.22 0 0 15 0 75.86 0 0 0 0 8.67 15.47 00 0 0 0 15 0 62.64 0 0 27.53 0 0 9.83 0 0 0 0 0 15 24.06 67.36 0 0 0 0 08.59 0 0 0 0 0 15 0 0 24.94 0 0 0 0 44.51 0 30.55 0 0 0 15 0 0 0 0 0 0 044.51 0 30.55 24.94 0 0 15 0 0 0 0 0 0 24.94 44.51 0 30.55 0 0 0 15 0 00 0 62.42 0 0 22.28 0 15.29 0 0 0 15 62.42 0 0 0 0 0 0 22.28 0 15.29 0 00 15 0 0 25 0 0 0 0 44.63 30.37 0 0 0 0 15 0 0 0 0 0 0 0 44.63 30.37 025 0 0 15 0 0 0 0 0 0 25 44.63 30.37 0 0 0 0 15 0 0 0 0 62.5 0 0 22.3115.19 0 0 0 0 15 62.5 0 0 0 0 0 0 22.31 15.19 0 0 0 0 15 0 0 0 0 0 0 0 00 0 0 0 0 16 0 58.48 11.7 0 0 0 0 29.82 0 0 0 0 0 16 0 71.14 0 0 0 0 020.73 0 0 8.13 0 0 16 0 77.88 0 0 0 0 6.23 15.89 0 0 0 0 0 16 0 68.28 00 21.01 0 0 10.71 0 0 0 0 0 16 18.15 72.6 0 0 0 0 0 9.26 0 0 0 0 0 16 00 18.15 0 0 0 0 46.28 0 35.57 0 0 0 16 0 0 0 0 0 0 0 46.28 0 35.57 18.150 0 16 0 0 0 0 0 0 18.15 46.28 0 35.57 0 0 0 16 0 0 0 0 52.58 0 0 26.810 20.61 0 0 0 16 52.58 0 0 0 0 0 0 26.81 0 20.61 0 0 0 16 0 0 18.2 0 0 00 46.41 35.38 0 0 0 0 16 0 0 0 0 0 0 0 46.41 35.38 0 18.2 0 0 16 0 0 0 00 0 18.2 46.41 35.38 0 0 0 0 16 0 0 0 0 52.66 0 0 26.86 20.48 0 0 0 0 1652.66 0 0 0 0 0 0 26.86 20.48 0 0 0 0 16 0 0 0 0 0 0 0 100 0 0 0 0 0

[0257] TABLE III R C COCONV H2OCONV CO2PROD CO2PERPROD CH4PROD Pt1.0%/ZrO2_std LaNO33 PtNH32NO22 ZrONO32 real real real real real realreal real real real real SUM_micromols mol % La mol % Pt mol % ZrTemperature: 250 C. 1 1 24.0554 20.3567 1.0059 36.8713 0.1785 0.1275 0 00 0.1275 0 100 0 1 2 −1.7201 3.3539 0.049 1.7972 0.0067 0 0 0 0 0 0 0 01 3 −1.3278 2.2499 0.0009 0.0315 −0.0026 0 0 0 0 0 0 0 0 1 4 −1.2082.4958 0.005 0.1823 −0.0038 0 0 0 0 0 0 0 0 1 5 −1.3966 −0.6647 0.01380.5067 −0.0024 0 0 0 0 0 0 0 0 1 6 −0.857 −0.806 0.0089 0.3249 −0.0058 00 0 0 0 0 0 0 1 7 26.8747 16.7142 0.9416 34.513 0.151 0.1275 0 0 00.1275 0 100 0 1 8 −0.1762 0.0001 0.0106 0.3868 −0.0076 0 0 0 0 0 0 0 01 9 −0.605 −1.4054 0.0016 0.0598 −0.0081 0 0 0 0 0 0 0 0 1 10 −0.17055.1803 −0.0005 −0.0171 −0.0108 0 0 0 0 0 0 0 0 1 11 0.0287 −2.3403−0.0261 −0.9568 −0.0134 0 0 0 0 0 0 0 0 1 12 −0.3619 −2.3753 −0.0191−0.6997 −0.0107 0 0 0 0 0 0 0 0 1 13 26.9134 15.6985 0.9206 33.74490.1456 0.1275 0 0 0 0.1275 0 100 0 1 14 0.2866 −1.4436 0.0104 0.3794−0.0009 0 0 0 0 0 0 0 0 1 15 −0.2691 −2.5021 −0.0098 −0.3592 −0.0125 0 00 0 0 0 0 0 1 16 26.3015 15.0776 0.9071 33.2485 0.1422 0.1275 0 0 00.1275 0 100 0 2 1 10.3797 7.5635 0.2714 9.9469 0.0465 0 0 0.0319 00.0319 0 100 0 2 2 22.2742 13.6256 0.7038 25.7961 0.1014 0 0 0.0319 00.0319 0 100 0 2 3 20.1518 11.8043 0.6181 22.6557 0.0925 0 0 0.0319 00.0319 0 100 0 2 4 14.7068 7.5278 0.4396 16.1127 0.074 0 0 0.0319 00.0319 0 100 0 2 5 12.5748 6.9812 0.3538 12.9691 0.0619 0 0 0.0319 00.0319 0 100 0 2 6 12.5733 7.5902 0.3721 13.6375 0.065 0 0 0.0319 00.0319 0 100 0 2 7 3.9682 1.1157 0.1053 3.861 0.0291 0 0 0.0319 0 0.03190 100 0 2 8 4.2902 1.5276 0.1017 3.728 0.0316 0 0 0.0319 0 0.0319 0 1000 2 9 17.5859 9.8527 0.5611 20.5685 0.0868 0 0 0.0319 0 0.0319 0 100 0 210 4.0056 0.7967 0.1073 3.9343 0.0337 0 0 0.0319 0 0.0319 0 100 0 2 110.4511 −1.4852 −0.0262 −0.9611 0.0142 0 0 0.0319 0 0.0319 0 100 0 2 128.7515 3.1358 0.2704 9.9096 0.0534 0 0 0.0319 0 0.0319 0 100 0 2 131.1667 −0.4291 0.0028 0.1022 0.0172 0 0 0.0319 0 0.0319 0 100 0 2 145.3788 3.039 0.1661 6.0891 0.0402 0 0 0.0319 0.625 0.6569 0 4.85 95.15 215 13.8175 7.9862 0.4538 16.6329 0.0753 0 0.625 0.0319 0 0.6569 95.154.85 0 2 16 0.5892 0.0397 −0.0171 −0.6274 −0.0021 0 0 0 0 0 0 0 0 3 123.0341 14.9411 0.7335 26.8867 0.1082 0 0 0.0387 0 0.0387 0 100 0 3 224.8268 16.0912 0.7611 27.8973 0.108 0 0 0.0387 0 0.0387 0 100 0 3 321.0312 12.2163 0.6617 24.2545 0.0974 0 0 0.0387 0 0.0387 0 100 0 3 415.3062 8.5994 0.4563 16.7247 0.0714 0 0 0.0387 0 0.0387 0 100 0 3 513.1818 6.4699 0.3775 13.8381 0.0651 0 0 0.0387 0 0.0387 0 100 0 3 614.4778 9.2713 0.4241 15.5437 0.0643 0 0 0.0387 0 0.0387 0 100 0 3 75.5717 3.3425 0.1029 3.772 0.0251 0 0 0.0387 0 0.0387 0 100 0 3 8 6.82281.6923 0.1521 5.5733 0.0283 0 0 0.0387 0 0.0387 0 100 0 3 9 18.242312.1678 0.5606 20.5468 0.0831 0 0 0.0387 0 0.0387 0 100 0 3 10 6.70115.5857 0.1612 5.907 0.033 0 0 0.0387 0 0.0387 0 100 0 3 11 1.3529 1.3312−0.0328 −1.2024 0.0065 0 0 0.0387 0 0.0387 0 100 0 3 12 8.988 6.94540.2544 9.3233 0.0421 0 0 0.0387 0 0.0387 0 100 0 3 13 1.9882 1.6201−0.0124 −0.4561 0.0102 0 0 0.0387 0 0.0387 0 100 0 3 14 6.7207 4.88020.1283 4.7036 0.0288 0 0 0.0387 0.625 0.6637 0 5.83 94.17 3 15 13.12547.8413 0.4144 15.1912 0.0623 0 0.625 0.0387 0 0.6637 94.17 5.83 0 3 161.6968 −0.6116 −0.0065 −0.238 0.007 0 0 0 0 0 0 0 0 4 1 25.6701 19.51970.7514 27.5411 0.0986 0 0 0.0455 0 0.0455 0 100 0 4 2 23.653 16.92270.7928 29.0607 0.0984 0 0 0.0455 0 0.0455 0 100 0 4 3 22.8118 16.18440.6593 24.168 0.0919 0 0 0.0455 0 0.0455 0 100 0 4 4 16.4182 10.78730.4837 17.731 0.0754 0 0 0.0455 0 0.0455 0 100 0 4 5 14.5564 7.51370.4146 15.1965 0.0579 0 0 0.0455 0 0.0455 0 100 0 4 6 15.7933 9.82730.453 16.6027 0.0657 0 0 0.0455 0 0.0455 0 100 0 4 7 6.1716 5.31920.1362 4.9935 0.0244 0 0 0.0455 0 0.0455 0 100 0 4 8 7.1386 3.68670.1822 6.6787 0.0338 0 0 0.0455 0 0.0455 0 100 0 4 9 20.7303 13.37340.6248 22.9033 0.0886 0 0 0.0455 0 0.0455 0 100 0 4 10 8.9131 3.1940.1982 7.2642 0.0334 0 0 0.0455 0 0.0455 0 100 0 4 11 1.6189 1.2404−0.0525 −1.926 −0.0002 0 0 0.0455 0 0.0455 0 100 0 4 12 10.7432 5.7820.2838 10.4022 0.045 0 0 0.0455 0 0.0455 0 100 0 4 13 1.5884 0.8166−0.0105 −0.3833 0.0101 0 0 0.0455 0 0.0455 0 100 0 4 14 6.4031 3.23360.1734 6.3554 0.0362 0 0 0.0455 0.625 0.6705 0 6.79 93.21 4 15 15.612510.3811 0.4713 17.2763 0.0703 0 0.625 0.0455 0 0.6705 93.21 6.79 0 4 1627.9195 15.9998 0.8541 31.3081 0.1277 0.1275 0 0 0 0.1275 0 100 0 5 123.5648 16.7387 0.7605 27.8743 0.1008 0 0 0.0524 0 0.0524 0 100 0 5 224.3053 17.3486 0.7802 28.5962 0.1046 0 0 0.0524 0 0.0524 0 100 0 5 322.341 15.7024 0.7107 26.0515 0.1019 0 0 0.0524 0 0.0524 0 100 0 5 417.6158 11.8733 0.5469 20.0479 0.0791 0 0 0.0524 0 0.0524 0 100 0 5 514.2387 10.1452 0.4049 14.8406 0.0574 0 0 0.0524 0 0.0524 0 100 0 5 615.1152 10.7747 0.4328 15.8622 0.0615 0 0 0.0524 0 0.0524 0 100 0 5 76.2094 5.1538 0.1363 4.9969 0.0249 0 0 0.0524 0 0.0524 0 100 0 5 87.6993 4.4249 0.2079 7.6192 0.0348 0 0 0.0524 0 0.0524 0 100 0 5 920.3032 12.9878 0.6687 24.5092 0.091 0 0 0.0524 0 0.0524 0 100 0 5 1010.467 7.0359 0.2642 9.6824 0.0427 0 0 0.0524 0 0.0524 0 100 0 5 112.8488 0.9928 −0.0496 −1.8191 −0.0034 0 0 0.0524 0 0.0524 0 100 0 5 128.6081 4.7427 0.2975 10.9032 0.0379 0 0 0.0524 0 0.0524 0 100 0 5 132.4786 0.2441 −0.0353 −1.2925 0.0105 0 0 0.0524 0 0.0524 0 100 0 5 145.1083 3.0311 0.1416 5.192 0.0285 0 0 0.0524 0.625 0.6774 0 7.73 92.27 515 11.8585 7.5495 0.3716 13.62 0.0576 0 0.625 0.0524 0 0.6774 92.27 7.730 5 16 0.172 0.0674 −0.0092 −0.3389 0.01 0 0 0 0 0 0 0 0 6 1 22.854815.2481 0.7655 28.0601 0.1096 0 0 0.0592 0 0.0592 0 100 0 6 2 25.420516.425 0.8006 29.3446 0.11 0 0 0.0592 0 0.0592 0 100 0 6 3 25.035916.7118 0.7742 28.379 0.1081 0 0 0.0592 0 0.0592 0 100 0 6 4 19.824213.56 0.6037 22.1285 0.0864 0 0 0.0592 0 0.0592 0 100 0 6 5 15.566710.9252 0.4506 16.5181 0.0668 0 0 0.0592 0 0.0592 0 100 0 6 6 14.92489.1668 0.4848 17.7684 0.0716 0 0 0.0592 0 0.0592 0 100 0 6 7 6.27484.0969 0.1824 6.6868 0.0317 0 0 0.0592 0 0.0592 0 100 0 6 8 8.48585.8883 0.251 9.2019 0.0404 0 0 0.0592 0 0.0592 0 100 0 6 9 21.002712.7923 0.7581 27.7862 0.1015 0 0 0.0592 0 0.0592 0 100 0 6 10 4.18641.0991 0.2231 8.177 0.044 0 0 0.0592 0 0.0592 0 100 0 6 11 −1.2373−1.4393 0.0135 0.4931 0.0092 0 0 0.0592 0 0.0592 0 100 0 6 12 10.62866.8786 0.3149 11.5433 0.0492 0 0 0.0592 0 0.0592 0 100 0 6 13 1.07160.1767 0.0081 0.2959 0.0131 0 0 0.0592 0 0.0592 0 100 0 6 14 6.69594.4786 0.1742 6.3849 0.0291 0 0 0.0592 0.625 0.6842 0 8.65 91.35 6 1514.9263 8.9373 0.4504 16.5076 0.0691 0 0.625 0.0592 0 0.6842 91.35 8.650 6 16 0.9734 0.524 −0.0068 −0.2476 0.0095 0 0 0 0 0 0 0 0 7 1 22.541815.4759 0.726 26.6121 0.0978 0 0 0.066 0 0.066 0 100 0 7 2 25.335217.1813 0.8109 29.7233 0.1123 0 0 0.066 0 0.066 0 100 0 7 3 25.457517.3091 0.7912 29.0012 0.1094 0 0 0.066 0 0.066 0 100 0 7 4 20.657214.3391 0.6313 23.1392 0.0896 0 0 0.066 0 0.066 0 100 0 7 5 15.93211.3449 0.4504 16.51 0.0654 0 0 0.066 0 0.066 0 100 0 7 6 15.786211.3444 0.4701 17.2316 0.0672 0 0 0.066 0 0.066 0 100 0 7 7 6.55185.4328 0.1609 5.8983 0.0264 0 0 0.066 0 0.066 0 100 0 7 8 8.798 5.74770.2274 8.3369 0.0394 0 0 0.066 0 0.066 0 100 0 7 9 23.0075 15.39250.6659 24.4074 0.0863 0 0 0.066 0 0.066 0 100 0 7 10 9.2334 7.39960.2983 10.934 0.0356 0 0 0.066 0 0.066 0 100 0 7 11 0.7033 0.897 −0.0323−1.1825 0.0007 0 0 0.066 0 0.066 0 100 0 7 12 9.8812 6.9932 0.310611.3832 0.047 0 0 0.066 0 0.066 0 100 0 7 13 1.8315 1.5281 −0.0004−0.0142 0.0064 0 0 0.066 0 0.066 0 100 0 7 14 5.9233 4.0164 0.13464.9347 0.024 0 0 0.066 0.625 0.691 0 9.55 90.45 7 15 11.3981 7.03520.3499 12.8255 0.0508 0 0.625 0.066 0 0.691 90.45 9.55 0 7 16 26.566916.7815 0.8474 31.0624 0.1182 0.1275 0 0 0 0.1275 0 100 0 8 1 22.720115.0948 0.694 25.4388 0.0942 0 0 0.0729 0 0.0729 0 100 0 8 2 25.596816.5345 0.8165 29.9286 0.1106 0 0 0.0729 0 0.0729 0 100 0 8 3 26.901516.5093 0.8118 29.7556 0.1132 0 0 0.0729 0 0.0729 0 100 0 8 4 22.691214.399 0.6735 24.6849 0.0922 0 0 0.0729 0 0.0729 0 100 0 8 5 16.151310.0868 0.4873 17.8622 0.0711 0 0 0.0729 0 0.0729 0 100 0 8 6 14.96049.3549 0.5104 18.7093 0.0788 0 0 0.0729 0 0.0729 0 100 0 8 7 9.11064.8845 0.1351 4.9537 0.0227 0 0 0.0729 0 0.0729 0 100 0 8 8 11.64454.2759 0.265 9.7129 0.0431 0 0 0.0729 0 0.0729 0 100 0 8 9 22.149613.0101 0.7517 27.5537 0.103 0 0 0.0729 0 0.0729 0 100 0 8 10 10.75747.0805 0.323 11.8395 0.0477 0 0 0.0729 0 0.0729 0 100 0 8 11 3.60040.9577 0.0383 1.4029 0.0094 0 0 0.0729 0 0.0729 0 100 0 8 12 11.5347.8883 0.3533 12.9484 0.0508 0 0 0.0729 0 0.0729 0 100 0 8 13 1.34640.5169 −0.0012 −0.0457 0.0054 0 0 0.0729 0 0.0729 0 100 0 8 14 6.40943.371 0.1695 6.2144 0.0276 0 0 0.0729 0.625 0.6979 0 10.44 89.56 8 1512.8137 8.3353 0.3838 14.067 0.054 0 0.625 0.0729 0 0.6979 89.56 10.44 08 16 0.6005 0.7618 −0.0245 −0.8983 0.0023 0 0 0 0 0 0 0 0 9 1 22.495714.7378 0.6826 25.0193 0.0926 0 0 0.0797 0 0.0797 0 100 0 9 2 25.98617.2218 0.8042 29.4787 0.1075 0 0 0.0797 0 0.0797 0 100 0 9 3 26.727817.0659 0.8299 30.4191 0.1155 0 0 0.0797 0 0.0797 0 100 0 9 4 21.782514.3953 0.6911 25.3306 0.0965 0 0 0.0797 0 0.0797 0 100 0 9 5 17.250811.3087 0.5012 18.3711 0.0717 0 0 0.0797 0 0.0797 0 100 0 9 6 16.958110.5872 0.4639 17.0022 0.0651 0 0 0.0797 0 0.0797 0 100 0 9 7 6.33354.0566 0.1665 6.1027 0.0326 0 0 0.0797 0 0.0797 0 100 0 9 8 11.94486.8015 0.2794 10.2426 0.0347 0 0 0.0797 0 0.0797 0 100 0 9 9 22.368214.3068 0.6953 25.4874 0.0927 0 0 0.0797 0 0.0797 0 100 0 9 10 10.63956.5727 0.3015 11.0498 0.0426 0 0 0.0797 0 0.0797 0 100 0 9 11 0.7463−0.5268 −0.0297 −1.0885 0.0037 0 0 0.0797 0 0.0797 0 100 0 9 12 11.64366.9032 0.3308 12.1271 0.0465 0 0 0.0797 0 0.0797 0 100 0 9 13 2.27341.3731 −0.0036 −0.1307 0.0063 0 0 0.0797 0 0.0797 0 100 0 9 14 5.24732.3383 0.133 4.8766 0.0256 0 0 0.0797 0.625 0.7047 0 11.31 88.69 9 1514.1744 8.1484 0.4386 16.0753 0.0629 0 0.625 0.0797 0 0.7047 88.69 11.310 9 16 1.1167 0.6406 −0.0074 −0.2708 0.0074 0 0 0 0 0 0 0 0 10 1 21.070614.7112 0.6846 25.0928 0.0968 0 0 0.0865 0 0.0865 0 100 0 10 2 26.886917.9825 0.8859 32.4724 0.1184 0 0 0.0865 0 0.0865 0 100 0 10 3 26.681316.9521 0.9023 33.0744 0.1263 0 0 0.0865 0 0.0865 0 100 0 10 4 22.852614.0275 0.7543 27.65 0.106 0 0 0.0865 0 0.0865 0 100 0 10 5 16.46439.638 0.5121 18.772 0.0768 0 0 0.0865 0 0.0865 0 100 0 10 6 16.97410.2305 0.4989 18.2853 0.0738 0 0 0.0865 0 0.0865 0 100 0 10 7 7.07643.7892 0.217 7.954 0.0367 0 0 0.0865 0 0.0865 0 100 0 10 8 10.33017.0156 0.3079 11.2846 0.0444 0 0 0.0865 0 0.0865 0 100 0 10 9 22.926514.8712 0.7519 27.5603 0.1024 0 0 0.0865 0 0.0865 0 100 0 10 10 12.46776.9963 0.3574 13.1014 0.0529 0 0 0.0865 0 0.0865 0 100 0 10 11 0.5969−0.5299 −0.0215 −0.7876 0.0033 0 0 0.0865 0 0.0865 0 100 0 10 12 13.33248.0107 0.3981 14.593 0.0579 0 0 0.0865 0 0.0865 0 100 0 10 13 1.90310.5698 0.0129 0.4715 0.0076 0 0 0.0865 0 0.0865 0 100 0 10 14 6.48473.7801 0.156 5.7172 0.0292 0 0 0.0865 0.625 0.7115 0 12.16 87.84 10 1513.3979 8.7146 0.4385 16.0738 0.0621 0 0.625 0.0865 0 0.7115 87.84 12.160 10 16 25.4495 16.0477 0.8342 30.5766 0.1176 0.1275 0 0 0 0.1275 0 1000 11 1 20.1375 13.3902 0.695 25.4752 0.0941 0 0 0.0933 0 0.0933 0 100 011 2 27.139 17.1786 0.8841 32.4048 0.1236 0 0 0.0933 0 0.0933 0 100 0 113 26.9388 16.683 0.9125 33.4483 0.127 0 0 0.0933 0 0.0933 0 100 0 11 424.5762 15.8875 0.789 28.9207 0.1089 0 0 0.0933 0 0.0933 0 100 0 11 515.1923 9.882 0.4773 17.4944 0.0718 0 0 0.0933 0 0.0933 0 100 0 11 615.7362 10.517 0.4959 18.1782 0.0704 0 0 0.0933 0 0.0933 0 100 0 11 76.9524 4.547 0.2149 7.8771 0.0338 0 0 0.0933 0 0.0933 0 100 0 11 810.7228 5.8543 0.3063 11.2265 0.0473 0 0 0.0933 0 0.0933 0 100 0 11 921.6871 13.7234 0.7381 27.0563 0.1017 0 0 0.0933 0 0.0933 0 100 0 11 1010.2552 6.749 0.3273 11.9961 0.0462 0 0 0.0933 0 0.0933 0 100 0 11 110.1751 −0.8137 −0.0162 −0.5948 0.0093 0 0 0.0933 0 0.0933 0 100 0 11 1212.9233 7.3461 0.3959 14.5118 0.058 0 0 0.0933 0 0.0933 0 100 0 11 132.1161 −0.0461 0.0196 0.7173 0.0121 0 0 0.0933 0 0.0933 0 100 0 11 145.318 2.5839 0.1421 5.2076 0.028 0 0 0.0933 0.625 0.7183 0 12.99 87.0111 15 12.7569 6.3017 0.3941 14.4456 0.0579 0 0.625 0.0933 0 0.7183 87.0112.99 0 11 16 0.8455 −1.3583 0.0027 0.0985 0.0084 0 0 0 0 0 0 0 0 12 115.9884 10.3576 0.5209 19.0939 0.0763 0 0 0.1002 0 0.1002 0 100 0 12 227.3984 16.7714 0.9241 33.8719 0.128 0 0 0.1002 0 0.1002 0 100 0 12 328.1625 17.4315 0.9325 34.1804 0.1313 0 0 0.1002 0 0.1002 0 100 0 12 424.8213 15.2594 0.851 31.1941 0.1246 0 0 0.1002 0 0.1002 0 100 0 12 516.5105 9.4519 0.5715 20.9463 0.089 0 0 0.1002 0 0.1002 0 100 0 12 616.2367 8.6629 0.5246 19.229 0.0791 0 0 0.1002 0 0.1002 0 100 0 12 77.0822 2.7268 0.2494 9.143 0.0433 0 0 0.1002 0 0.1002 0 100 0 12 811.1025 6.1665 0.3763 13.7941 0.056 0 0 0.1002 0 0.1002 0 100 0 12 923.5429 14.4559 0.8026 29.419 0.1129 0 0 0.1002 0 0.1002 0 100 0 12 1012.4169 7.2141 0.384 14.0754 0.0576 0 0 0.1002 0 0.1002 0 100 0 12 11−0.2192 −1.5288 −0.0114 −0.4195 0.0063 0 0 0.1002 0 0.1002 0 100 0 12 1213.2567 7.0496 0.4182 15.3281 0.0611 0 0 0.1002 0 0.1002 0 100 0 12 131.2187 −0.6308 0.0286 1.0496 0.0116 0 0 0.1002 0 0.1002 0 100 0 12 145.5276 1.9229 0.1649 6.0426 0.0328 0 0 0.1002 0.625 0.7252 0 13.81 86.1912 15 13.3469 6.2659 0.4232 15.5137 0.0634 0 0.625 0.1002 0 0.7252 86.1913.81 0 12 16 1.0083 −0.586 0.011 0.4039 0.0096 0 0 0 0 0 0 0 0 13 118.6644 11.2964 0.6506 23.8458 0.0932 0 0 0.107 0 0.107 0 100 0 13 227.845 15.9413 0.9392 34.4261 0.1308 0 0 0.107 0 0.107 0 100 0 13 327.3697 17.3186 0.9442 34.6097 0.1337 0 0 0.107 0 0.107 0 100 0 13 425.678 15.9207 0.8401 30.7915 0.1183 0 0 0.107 0 0.107 0 100 0 13 515.7945 10.0005 0.5228 19.164 0.0793 0 0 0.107 0 0.107 0 100 0 13 615.3463 9.2398 0.5087 18.6471 0.0765 0 0 0.107 0 0.107 0 100 0 13 76.7754 3.6609 0.2308 8.459 0.0396 0 0 0.107 0 0.107 0 100 0 13 8 11.6926.4553 0.3752 13.7513 0.0561 0 0 0.107 0 0.107 0 100 0 13 9 23.280913.521 0.8112 29.7353 0.1124 0 0 0.107 0 0.107 0 100 0 13 10 13.55627.5286 0.4302 15.7676 0.0624 0 0 0.107 0 0.107 0 100 0 13 11 1.1357−1.0497 −0.0258 −0.9457 0.0072 0 0 0.107 0 0.107 0 100 0 13 12 14.08927.0847 0.4404 16.1411 0.0683 0 0 0.107 0 0.107 0 100 0 13 13 1.2307−0.0972 0.0411 1.5048 0.0161 0 0 0.107 0 0.107 0 100 0 13 14 5.04731.1814 0.1519 5.5685 0.0306 0 0 0.107 0.625 0.732 0 14.62 85.38 13 1512.8894 6.9657 0.3932 14.413 0.0574 0 0.625 0.107 0 0.732 85.38 14.62 013 16 27.0196 15.8321 0.9126 33.449 0.1349 0.1275 0 0 0 0.1275 0 100 014 1 21.6824 14.5808 0.7642 28.0108 0.1054 0 0 0.1138 0 0.1138 0 100 014 2 27.9534 18.5673 0.9122 33.4357 0.1269 0 0 0.1138 0 0.1138 0 100 014 3 28.3871 17.6025 0.9506 34.8433 0.1361 0 0 0.1138 0 0.1138 0 100 014 4 26.5322 15.1329 0.8627 31.6204 0.1283 0 0 0.1138 0 0.1138 0 100 014 5 17.27 10.4633 0.5486 20.1091 0.0846 0 0 0.1138 0 0.1138 0 100 0 146 16.6826 9.6418 0.5721 20.9704 0.0848 0 0 0.1138 0 0.1138 0 100 0 14 77.7667 4.5307 0.2694 9.8752 0.0433 0 0 0.1138 0 0.1138 0 100 0 14 813.2575 8.5866 0.4374 16.0317 0.064 0 0 0.1138 0 0.1138 0 100 0 14 924.5972 16.2327 0.8255 30.2566 0.1118 0 0 0.1138 0 0.1138 0 100 0 14 1014.1237 8.1483 0.478 17.5191 0.0713 0 0 0.1138 0 0.1138 0 100 0 14 11−0.172 −1.5106 −0.0204 −0.7482 0.0089 0 0 0.1138 0 0.1138 0 100 0 14 1215.8277 8.9664 0.5076 18.6043 0.0706 0 0 0.1138 0 0.1138 0 100 0 14 131.0637 −1.0104 0.0444 1.6268 0.0139 0 0 0.1138 0 0.1138 0 100 0 14 144.6635 2.3532 0.1677 6.1462 0.0296 0 0 0.1138 0.625 0.7388 0 15.41 84.5914 15 12.9488 7.3298 0.4296 15.7453 0.0651 0 0.625 0.1138 0 0.7388 84.5915.41 0 14 16 0.3061 −0.5069 −0.0065 −0.2391 0.0099 0 0 0 0 0 0 0 0 15 117.1998 12.0104 0.5755 21.0955 0.0799 0 0 0.1207 0 0.1207 0 100 0 15 227.4482 17.526 0.933 34.1967 0.1316 0 0 0.1207 0 0.1207 0 100 0 15 328.1178 18.8556 0.9242 33.8763 0.1324 0 0 0.1207 0 0.1207 0 100 0 15 426.8701 17.1463 0.856 31.3778 0.1258 0 0 0.1207 0 0.1207 0 100 0 15 517.6631 10.9667 0.5845 21.4248 0.0858 0 0 0.1207 0 0.1207 0 100 0 15 617.1402 10.8854 0.5425 19.8853 0.0798 0 0 0.1207 0 0.1207 0 100 0 15 78.2663 5.3027 0.2441 8.9487 0.0387 0 0 0.1207 0 0.1207 0 100 0 15 811.9892 6.7241 0.3904 14.3081 0.0566 0 0 0.1207 0 0.1207 0 100 0 15 924.1606 15.639 0.8291 30.3902 0.1118 0 0 0.1207 0 0.1207 0 100 0 15 1015.0377 10.3936 0.4614 16.9136 0.0638 0 0 0.1207 0 0.1207 0 100 0 15 110.2191 −0.9933 −0.0152 −0.558 0.0074 0 0 0.1207 0 0.1207 0 100 0 15 1216.1138 9.1228 0.5094 18.6707 0.0732 0 0 0.1207 0 0.1207 0 100 0 15 132.4821 0.3422 0.0309 1.1317 0.0144 0 0 0.1207 0 0.1207 0 100 0 15 145.4454 0.6463 0.189 6.9276 0.035 0 0 0.1207 0.625 0.7457 0 16.18 83.8215 15 14.0229 7.8558 0.4492 16.4654 0.0681 0 0.625 0.1207 0 0.7457 83.8216.18 0 15 16 0.4686 −0.7131 0.0197 0.7216 0.01 0 0 0 0 0 0 0 0 16 17.4861 4.4402 0.2493 9.1386 0.0401 0 0 0.1275 0 0.1275 0 100 0 16 229.0506 17.8613 0.9483 34.7579 0.1412 0 0 0.1275 0 0.1275 0 100 0 16 329.4694 17.4993 0.9236 33.8554 0.1479 0 0 0.1275 0 0.1275 0 100 0 16 428.4749 16.4322 0.9104 33.3693 0.1531 0 0 0.1275 0 0.1275 0 100 0 16 522.0326 12.6858 0.7055 25.8606 0.1115 0 0 0.1275 0 0.1275 0 100 0 16 620.0805 12.1402 0.6291 23.0594 0.0943 0 0 0.1275 0 0.1275 0 100 0 16 79.0587 5.2161 0.2666 9.7703 0.0461 0 0 0.1275 0 0.1275 0 100 0 16 813.983 9.3075 0.4391 16.0948 0.0636 0 0 0.1275 0 0.1275 0 100 0 16 926.9905 17.0719 0.877 32.1456 0.1198 0 0 0.1275 0 0.1275 0 100 0 16 1014.704 8.6762 0.4886 17.9102 0.073 0 0 0.1275 0 0.1275 0 100 0 16 110.7191 −1.4742 −0.0041 −0.1519 0.0077 0 0 0.1275 0 0.1275 0 100 0 16 1219.314 11.1355 0.6495 23.808 0.0899 0 0 0.1275 0 0.1275 0 100 0 16 132.4636 0.033 0.0679 2.4886 0.0206 0 0 0.1275 0 0.1275 0 100 0 16 1411.4461 6.8975 0.3856 14.134 0.0639 0 0 0.1275 0.625 0.7525 0 16.9483.06 16 15 20.8264 13.1623 0.7 25.6595 0.0961 0 0.625 0.1275 0 0.752583.06 16.94 0 16 16 26.7851 15.9945 0.9048 33.1661 0.1319 0.1275 0 0 00.1275 0 100 0 Temperature: 300 C. 1 1 26.0412 13.6761 0.7608 27.43270.1592 0.1275 0 0 0 0.1275 0 100 0 1 2 1.9716 2.4686 0.0066 0.23860.0092 0 0 0 0 0 0 0 0 1 3 0.3229 0.3952 −0.0391 −1.4081 0.0062 0 0 0 00 0 0 0 1 4 0.6417 0.8578 −0.0504 −1.8187 −0.0005 0 0 0 0 0 0 0 0 1 50.173 0.5233 −0.0449 −1.6183 0.0024 0 0 0 0 0 0 0 0 1 6 0.3624 0.0747−0.0376 −1.3546 −0.0039 0 0 0 0 0 0 0 0 1 7 26.157 12.3934 0.797 28.73830.1699 0.1275 0 0 0 0.1275 0 100 0 1 8 3.5333 0.2801 −0.0585 −2.108−0.0107 0 0 0 0 0 0 0 0 1 9 −1.8657 −3.8002 −0.0104 −0.375 0.0197 0 0 00 0 0 0 0 1 10 2.592 0.129 −0.014 −0.5051 −0.0253 0 0 0 0 0 0 0 0 1 11−3.1613 −1.397 −0.0273 −0.9858 0.0043 0 0 0 0 0 0 0 0 1 12 −0.5382−0.741 −0.0195 −0.7042 −0.0352 0 0 0 0 0 0 0 0 1 13 25.293 12.93310.8097 29.194 0.1597 0.1275 0 0 0 0.1275 0 100 0 1 14 0.8774 0.3654−0.018 −0.648 0.0052 0 0 0 0 0 0 0 0 1 15 −1.2793 0.1383 −0.0181 −0.65430.0027 0 0 0 0 0 0 0 0 1 16 25.6735 12.143 0.7277 26.2368 0.1566 0.12750 0 0 0.1275 0 100 0 2 1 14.8766 10.2106 0.3917 14.1217 0.0524 0 00.0319 0 0.0319 0 100 0 2 2 20.4545 14.6181 0.746 26.8969 0.1088 0 00.0319 0 0.0319 0 100 0 2 3 19.9352 12.3858 0.6977 25.1579 0.1196 0 00.0319 0 0.0319 0 100 0 2 4 16.0396 10.1097 0.6511 23.4768 0.109 0 00.0319 0 0.0319 0 100 0 2 5 15.904 10.2101 0.4597 16.5765 0.0626 0 00.0319 0 0.0319 0 100 0 2 6 14.9915 9.8692 0.3995 14.4034 0.0662 0 00.0319 0 0.0319 0 100 0 2 7 6.2101 5.2473 0.1852 6.6763 0.0252 0 00.0319 0 0.0319 0 100 0 2 8 9.4972 5.8339 0.283 10.205 0.0496 0 0 0.03190 0.0319 0 100 0 2 9 21.1669 13.9111 0.6435 23.2016 0.0932 0 0 0.0319 00.0319 0 100 0 2 10 8.0932 5.8934 0.2958 10.6661 0.0493 0 0 0.0319 00.0319 0 100 0 2 11 0.4906 0.3109 −0.0754 −2.7173 0.0004 0 0 0.0319 00.0319 0 100 0 2 12 12.7979 8.96 0.445 16.0439 0.0703 0 0 0.0319 00.0319 0 100 0 2 13 1.7683 2.1621 0.0286 1.0326 0.0176 0 0 0.0319 00.0319 0 100 0 2 14 11.5049 8.9483 0.3603 12.9899 0.0656 0 0 0.03190.625 0.6569 0 4.85 95.15 2 15 19.2509 11.5249 0.6541 23.5849 0.0881 00.625 0.0319 0 0.6569 95.15 4.85 0 2 16 −2.2275 0.1022 0.0038 0.1360.001 0 0 0 0 0 0 0 0 3 1 19.5625 13.7405 0.7553 27.2322 0.1169 0 00.0387 0 0.0387 0 100 0 3 2 23.3448 16.4986 0.7782 28.0599 0.1055 0 00.0387 0 0.0387 0 100 0 3 3 20.2746 14.4888 0.7447 26.8513 0.1236 0 00.0387 0 0.0387 0 100 0 3 4 21.042 14.6567 0.5975 21.5435 0.0868 0 00.0387 0 0.0387 0 100 0 3 5 15.227 11.3009 0.5184 18.6931 0.0896 0 00.0387 0 0.0387 0 100 0 3 6 16.2981 13.1574 0.4916 17.7266 0.0804 0 00.0387 0 0.0387 0 100 0 3 7 7.5318 7.7146 0.2177 7.8495 0.0364 0 00.0387 0 0.0387 0 100 0 3 8 14.1025 10.9954 0.419 15.1061 0.0628 0 00.0387 0 0.0387 0 100 0 3 9 20.9253 15.3432 0.7024 25.3266 0.1019 0 00.0387 0 0.0387 0 100 0 3 10 13.728 11.1605 0.4466 16.1033 0.0679 0 00.0387 0 0.0387 0 100 0 3 11 −1.0656 0.7638 −0.03 −1.0824 −0.001 0 00.0387 0 0.0387 0 100 0 3 12 12.0316 9.0087 0.4143 14.9372 0.064 0 00.0387 0 0.0387 0 100 0 3 13 2.3735 2.427 0.0472 1.7003 0.0158 0 00.0387 0 0.0387 0 100 0 3 14 10.011 6.6184 0.4321 15.5784 0.078 0 00.0387 0.625 0.6637 0 5.83 94.17 3 15 17.1288 11.9418 0.6936 25.00810.1016 0 0.625 0.0387 0 0.6637 94.17 5.83 0 3 16 −0.0207 −0.0056 0.05642.0341 −0.003 0 0 0 0 0 0 0 0 4 1 23.9972 15.9845 0.7717 27.8233 0.119 00 0.0455 0 0.0455 0 100 0 4 2 24.3635 16.2531 0.7072 25.5007 0.1199 0 00.0455 0 0.0455 0 100 0 4 3 21.4425 14.1432 0.7498 27.0362 0.1265 0 00.0455 0 0.0455 0 100 0 4 4 19.4479 12.996 0.6822 24.5996 0.107 0 00.0455 0 0.0455 0 100 0 4 5 16.0527 11.3163 0.5819 20.98 0.0935 0 00.0455 0 0.0455 0 100 0 4 6 17.5309 11.186 0.5671 20.447 0.0842 0 00.0455 0 0.0455 0 100 0 4 7 8.0993 5.7381 0.3374 12.166 0.0503 0 00.0455 0 0.0455 0 100 0 4 8 14.119 9.8107 0.5489 19.7929 0.0801 0 00.0455 0 0.0455 0 100 0 4 9 23.2762 14.9011 0.7786 28.0723 0.1033 0 00.0455 0 0.0455 0 100 0 4 10 14.7194 10.4363 0.5718 20.6185 0.08 0 00.0455 0 0.0455 0 100 0 4 11 1.1453 0.3882 −0.067 −2.4162 −0.0168 0 00.0455 0 0.0455 0 100 0 4 12 12.7656 8.8311 0.4759 17.1582 0.0689 0 00.0455 0 0.0455 0 100 0 4 13 4.4502 1.323 0.0072 0.2593 0.0135 0 00.0455 0 0.0455 0 100 0 4 14 13.3844 9.4729 0.4141 14.9311 0.0687 0 00.0455 0.625 0.6705 0 6.79 93.21 4 15 20.7018 14.4153 0.6795 24.50020.0932 0 0.625 0.0455 0 0.6705 93.21 6.79 0 4 16 26.3093 12.5646 0.740526.6988 0.1561 0.1275 0 0 0 0.1275 0 100 0 5 1 21.4105 14.4067 0.712525.6898 0.11 0 0 0.0524 0 0.0524 0 100 0 5 2 22.1022 14.8036 0.81929.5304 0.1282 0 0 0.0524 0 0.0524 0 100 0 5 3 22.5933 14.8442 0.724426.1201 0.1233 0 0 0.0524 0 0.0524 0 100 0 5 4 21.0057 13.8057 0.691124.9201 0.1153 0 0 0.0524 0 0.0524 0 100 0 5 5 17.672 12.2393 0.572820.6522 0.0902 0 0 0.0524 0 0.0524 0 100 0 5 6 16.0245 11.7967 0.590221.2789 0.0941 0 0 0.0524 0 0.0524 0 100 0 5 7 8.682 6.8022 0.35 12.61850.0569 0 0 0.0524 0 0.0524 0 100 0 5 8 16.2047 10.7313 0.5656 20.39210.0857 0 0 0.0524 0 0.0524 0 100 0 5 9 21.0729 14.0649 0.7974 28.75150.124 0 0 0.0524 0 0.0524 0 100 0 5 10 18.1655 12.1093 0.6249 22.53230.094 0 0 0.0524 0 0.0524 0 100 0 5 11 −3.2789 −1.8833 0.0173 0.625−0.017 0 0 0.0524 0 0.0524 0 100 0 5 12 12.1376 7.6528 0.5085 18.33390.0689 0 0 0.0524 0 0.0524 0 100 0 5 13 2.8719 1.6064 0.0398 1.43470.0232 0 0 0.0524 0 0.0524 0 100 0 5 14 11.6313 7.1984 0.3756 13.54420.064 0 0 0.0524 0.625 0.6774 0 7.73 92.27 5 15 18.7077 12.3422 0.678424.4596 0.1017 0 0.625 0.0524 0 0.6774 92.27 7.73 0 5 16 −0.923 0.64230.0024 0.0871 −0.0005 0 0 0 0 0 0 0 0 6 1 22.0063 14.1082 0.7772 28.02160.121 0 0 0.0592 0 0.0592 0 100 0 6 2 23.7522 14.4251 0.8181 29.49830.1363 0 0 0.0592 0 0.0592 0 100 0 6 3 23.7349 12.7968 0.778 28.05180.1487 0 0 0.0592 0 0.0592 0 100 0 6 4 21.7688 12.1769 0.7488 27.00060.1335 0 0 0.0592 0 0.0592 0 100 0 6 5 18.6185 12.368 0.6292 22.68620.1057 0 0 0.0592 0 0.0592 0 100 0 6 6 17.435 11.7025 0.6457 23.28330.0997 0 0 0.0592 0 0.0592 0 100 0 6 7 9.5496 7.4033 0.4005 14.44180.0656 0 0 0.0592 0 0.0592 0 100 0 6 8 18.8345 12.608 0.602 21.70770.0895 0 0 0.0592 0 0.0592 0 100 0 6 9 22.7783 14.5707 0.7858 28.33190.1268 0 0 0.0592 0 0.0592 0 100 0 6 10 14.2889 9.3319 0.4808 17.33440.0626 0 0 0.0592 0 0.0592 0 100 0 6 11 −1.4423 −3.1898 0.0072 0.2597−0.0242 0 0 0.0592 0 0.0592 0 100 0 6 12 14.6391 9.1343 0.5169 18.63930.0784 0 0 0.0592 0 0.0592 0 100 0 6 13 1.3924 0.1849 0.1067 3.84580.0254 0 0 0.0592 0 0.0592 0 100 0 6 14 12.4467 7.9011 0.47 16.9470.0796 0 0 0.0592 0.625 0.6842 0 8.65 91.35 6 15 20.5551 12.4877 0.724126.1085 0.1086 0 0.625 0.0592 0 0.6842 91.35 8.65 0 6 16 1.8224 1.91940.0293 1.0577 −0.001 0 0 0 0 0 0 0 0 7 1 20.1793 13.5157 0.7141 25.74830.1062 0 0 0.066 0 0.066 0 100 0 7 2 23.9199 15.0715 0.7923 28.56910.1334 0 0 0.066 0 0.066 0 100 0 7 3 24.0921 13.8724 0.7704 27.77940.1489 0 0 0.066 0 0.066 0 100 0 7 4 22.4883 13.3333 0.7472 26.94010.1331 0 0 0.066 0 0.066 0 100 0 7 5 18.3753 10.967 0.6933 24.99640.1147 0 0 0.066 0 0.066 0 100 0 7 6 19.1636 11.8882 0.594 21.41790.0973 0 0 0.066 0 0.066 0 100 0 7 7 11.6242 8.7829 0.358 12.9075 0.05890 0 0.066 0 0.066 0 100 0 7 8 18.9461 11.9304 0.6075 21.9057 0.0865 0 00.066 0 0.066 0 100 0 7 9 20.8727 13.268 0.8581 30.9391 0.1366 0 0 0.0660 0.066 0 100 0 7 10 19.7469 12.533 0.627 22.6084 0.0889 0 0 0.066 00.066 0 100 0 7 11 0.2661 −1.0746 −0.0206 −0.7417 −0.0241 0 0 0.066 00.066 0 100 0 7 12 14.9635 8.7674 0.5117 18.4485 0.0776 0 0 0.066 00.066 0 100 0 7 13 2.473 1.1259 0.0915 3.3004 0.0134 0 0 0.066 0 0.066 0100 0 7 14 10.4908 6.4436 0.4097 14.774 0.0771 0 0 0.066 0.625 0.691 09.55 90.45 7 15 17.9387 11.3159 0.7335 26.449 0.109 0 0.625 0.066 00.691 90.45 9.55 0 7 16 24.6649 12.1883 0.7892 28.4564 0.1735 0.1275 0 00 0.1275 0 100 0 8 1 20.4072 13.9072 0.7031 25.3521 0.1107 0 0 0.0729 00.0729 0 100 0 8 2 23.2299 15.5533 0.8078 29.1272 0.1368 0 0 0.0729 00.0729 0 100 0 8 3 24.3029 13.9797 0.7799 28.1203 0.1564 0 0 0.0729 00.0729 0 100 0 8 4 22.2113 14.5975 0.7495 27.0256 0.1425 0 0 0.0729 00.0729 0 100 0 8 5 18.1577 13.0692 0.6943 25.034 0.1167 0 0 0.0729 00.0729 0 100 0 8 6 16.4584 11.241 0.6799 24.5135 0.1128 0 0 0.0729 00.0729 0 100 0 8 7 11.3178 9.6452 0.4321 15.5795 0.0596 0 0 0.0729 00.0729 0 100 0 8 8 20.8336 14.4605 0.6457 23.2815 0.0922 0 0 0.0729 00.0729 0 100 0 8 9 23.346 15.3942 0.8346 30.0941 0.1169 0 0 0.0729 00.0729 0 100 0 8 10 20.3283 13.3467 0.6964 25.1102 0.1063 0 0 0.0729 00.0729 0 100 0 8 11 6.0017 3.7447 0.2344 8.4523 0.0402 0 0 0.0729 00.0729 0 100 0 8 12 14.0669 9.2173 0.572 20.6246 0.0862 0 0 0.0729 00.0729 0 100 0 8 13 0.4343 −0.3379 0.1029 3.7103 0.0224 0 0 0.0729 00.0729 0 100 0 8 14 12.9196 8.2041 0.4689 16.9054 0.0749 0 0 0.07290.625 0.6979 0 10.44 89.56 8 15 20.3025 12.6472 0.6618 23.8639 0.1 00.625 0.0729 0 0.6979 89.56 10.44 0 8 16 0.7273 0.7062 −0.0175 −0.63−0.0087 0 0 0 0 0 0 0 0 9 1 19.0866 13.801 0.6956 25.0805 0.1067 0 00.0797 0 0.0797 0 100 0 9 2 23.4011 15.4022 0.8062 29.0677 0.1362 0 00.0797 0 0.0797 0 100 0 9 3 24.2636 14.0356 0.8069 29.094 0.1585 0 00.0797 0 0.0797 0 100 0 9 4 23.0618 13.7204 0.7603 27.4122 0.137 0 00.0797 0 0.0797 0 100 0 9 5 19.2953 12.3324 0.6838 24.6546 0.1191 0 00.0797 0 0.0797 0 100 0 9 6 16.4524 11.6941 0.5833 21.033 0.0966 0 00.0797 0 0.0797 0 100 0 9 7 8.8155 6.193 0.4081 14.7154 0.0678 0 00.0797 0 0.0797 0 100 0 9 8 18.3421 12.4823 0.6492 23.4094 0.095 0 00.0797 0 0.0797 0 100 0 9 9 22.5571 15.4221 0.8241 29.7153 0.1201 0 00.0797 0 0.0797 0 100 0 9 10 18.2863 13.1397 0.6724 24.2444 0.0988 0 00.0797 0 0.0797 0 100 0 9 11 −1.5339 −0.5868 −0.0006 −0.0218 −0.0198 0 00.0797 0 0.0797 0 100 0 9 12 13.9602 9.1693 0.5547 20.0022 0.0819 0 00.0797 0 0.0797 0 100 0 9 13 1.1827 1.2849 0.1107 3.9916 0.0024 0 00.0797 0 0.0797 0 100 0 9 14 10.2757 6.1288 0.3969 14.3106 0.0711 0 00.0797 0.625 0.7047 0 11.31 88.69 9 15 19.4095 11.4849 0.732 26.39180.1116 0 0.625 0.0797 0 0.7047 88.69 11.31 0 9 16 −0.4746 0.3 0.06492.3389 0.0106 0 0 0 0 0 0 0 0 10 1 19.6155 13.2592 0.7151 25.784 0.11370 0 0.0865 0 0.0865 0 100 0 10 2 24.4255 14.2114 0.8452 30.474 0.1541 00 0.0865 0 0.0865 0 100 0 10 3 25.1167 12.0723 0.8229 29.6706 0.1783 0 00.0865 0 0.0865 0 100 0 10 4 23.9367 12.0867 0.8302 29.934 0.1595 0 00.0865 0 0.0865 0 100 0 10 5 20.499 11.2772 0.6949 25.0561 0.1257 0 00.0865 0 0.0865 0 100 0 10 6 18.4277 10.342 0.652 23.5077 0.1136 0 00.0865 0 0.0865 0 100 0 10 7 10.6829 8.2331 0.4943 17.8212 0.0797 0 00.0865 0 0.0865 0 100 0 10 8 21.0351 13.5697 0.6934 25.0025 0.1016 0 00.0865 0 0.0865 0 100 0 10 9 23.3546 15.5724 0.8319 29.9961 0.1265 0 00.0865 0 0.0865 0 100 0 10 10 20.2733 13.206 0.7226 26.0547 0.1094 0 00.0865 0 0.0865 0 100 0 10 11 −2.2709 −1.6818 −0.003 −0.1081 −0.0191 0 00.0865 0 0.0865 0 100 0 10 12 15.5394 9.154 0.5767 20.7948 0.0875 0 00.0865 0 0.0865 0 100 0 10 13 2.338 0.6958 0.1166 4.204 0.0286 0 00.0865 0 0.0865 0 100 0 10 14 11.8371 7.0502 0.4485 16.1702 0.0781 0 00.0865 0.625 0.7115 0 12.16 87.84 10 15 18.9643 11.9052 0.7159 25.81250.1082 0 0.625 0.0865 0 0.7115 87.84 12.16 0 10 16 23.3683 12.03280.7792 28.0962 0.1577 0.1275 0 0 0 0.1275 0 100 0 11 1 18.6802 11.57420.6796 24.5045 0.1057 0 0 0.0933 0 0.0933 0 100 0 11 2 25.0222 13.98630.8039 28.9852 0.1512 0 0 0.0933 0 0.0933 0 100 0 11 3 25.6394 13.12150.8122 29.2838 0.1687 0 0 0.0933 0 0.0933 0 100 0 11 4 24.6744 14.51830.7802 28.132 0.1536 0 0 0.0933 0 0.0933 0 100 0 11 5 19.3295 12.61350.685 24.6995 0.1225 0 0 0.0933 0 0.0933 0 100 0 11 6 18.7665 11.78230.6491 23.4044 0.1112 0 0 0.0933 0 0.0933 0 100 0 11 7 12.0459 8.2620.4669 16.8355 0.0746 0 0 0.0933 0 0.0933 0 100 0 11 8 19.7356 12.29240.7225 26.0526 0.1072 0 0 0.0933 0 0.0933 0 100 0 11 9 23.3494 14.41310.8518 30.7139 0.1298 0 0 0.0933 0 0.0933 0 100 0 11 10 19.1323 12.68490.7094 25.5779 0.105 0 0 0.0933 0 0.0933 0 100 0 11 11 −0.9895 −0.2695−0.004 −0.1435 −0.0127 0 0 0.0933 0 0.0933 0 100 0 11 12 14.8304 10.19630.582 20.9867 0.0899 0 0 0.0933 0 0.0933 0 100 0 11 13 2.208 2.55870.1029 3.7107 0.0204 0 0 0.0933 0 0.0933 0 100 0 11 14 10.9763 6.42660.3918 14.1258 0.0707 0 0 0.0933 0.625 0.7183 0 12.99 87.01 11 1518.1906 10.6621 0.698 25.1685 0.106 0 0.625 0.0933 0 0.7183 87.01 12.990 11 16 −0.9643 −0.7161 0.0392 1.4143 −0.0048 0 0 0 0 0 0 0 0 12 115.4588 10.1833 0.5953 21.4632 0.1001 0 0 0.1002 0 0.1002 0 100 0 12 224.7319 13.6012 0.8478 30.5688 0.161 0 0 0.1002 0 0.1002 0 100 0 12 326.8912 12.8758 0.8008 28.8754 0.1851 0 0 0.1002 0 0.1002 0 100 0 12 424.6558 12.9216 0.8196 29.5504 0.1758 0 0 0.1002 0 0.1002 0 100 0 12 520.5267 12.1018 0.7215 26.0139 0.1329 0 0 0.1002 0 0.1002 0 100 0 12 618.4287 11.4481 0.6811 24.5589 0.1172 0 0 0.1002 0 0.1002 0 100 0 12 713.4393 9.372 0.4909 17.6995 0.0793 0 0 0.1002 0 0.1002 0 100 0 12 821.0809 13.9911 0.7512 27.0875 0.111 0 0 0.1002 0 0.1002 0 100 0 12 923.772 15.0448 0.8517 30.7084 0.1339 0 0 0.1002 0 0.1002 0 100 0 12 1019.8095 12.8912 0.7381 26.6137 0.1093 0 0 0.1002 0 0.1002 0 100 0 12 11−1.4941 −1.399 −0.0134 −0.4846 −0.018 0 0 0.1002 0 0.1002 0 100 0 12 1216.0743 10.6539 0.5977 21.5507 0.092 0 0 0.1002 0 0.1002 0 100 0 12 132.0581 1.6359 0.1105 3.986 0.0298 0 0 0.1002 0 0.1002 0 100 0 12 1410.744 6.4761 0.4184 15.0852 0.076 0 0 0.1002 0.625 0.7252 0 13.81 86.1912 15 18.2843 10.3265 0.6975 25.1492 0.112 0 0.625 0.1002 0 0.7252 86.1913.81 0 12 16 −0.4083 −1.1083 0.0632 2.2805 0.02 0 0 0 0 0 0 0 0 13 117.3784 11.3659 0.6531 23.5471 0.1026 0 0 0.107 0 0.107 0 100 0 13 224.8735 13.9698 0.8645 31.1714 0.1634 0 0 0.107 0 0.107 0 100 0 13 326.731 13.2379 0.8304 29.9397 0.1799 0 0 0.107 0 0.107 0 100 0 13 425.0125 13.3208 0.8199 29.5626 0.1706 0 0 0.107 0 0.107 0 100 0 13 520.9959 12.5637 0.7 25.2389 0.1263 0 0 0.107 0 0.107 0 100 0 13 619.7859 13.0643 0.6384 23.0182 0.1112 0 0 0.107 0 0.107 0 100 0 13 712.7701 8.6484 0.4737 17.0786 0.0821 0 0 0.107 0 0.107 0 100 0 13 819.9798 12.3643 0.7421 26.7561 0.1113 0 0 0.107 0 0.107 0 100 0 13 923.9004 15.4262 0.8368 30.1725 0.1326 0 0 0.107 0 0.107 0 100 0 13 1020.1688 14.395 0.7685 27.7093 0.1134 0 0 0.107 0 0.107 0 100 0 13 11−1.5531 −0.2131 0.0003 0.0093 −0.0139 0 0 0.107 0 0.107 0 100 0 13 1216.261 10.9519 0.6007 21.66 0.0928 0 0 0.107 0 0.107 0 100 0 13 132.1579 1.7026 0.1307 4.7131 0.0287 0 0 0.107 0 0.107 0 100 0 13 1410.3449 7.0881 0.4013 14.4697 0.0725 0 0 0.107 0.625 0.732 0 14.62 85.3813 15 17.9906 12.3676 0.6892 24.8485 0.1057 0 0.625 0.107 0 0.732 85.3814.62 0 13 16 24.9296 12.3107 0.7853 28.3135 0.1895 0.1275 0 0 0 0.12750 100 0 14 1 19.7006 13.895 0.7196 25.9447 0.1225 0 0 0.1138 0 0.1138 0100 0 14 2 24.628 13.7864 0.8645 31.1715 0.1715 0 0 0.1138 0 0.1138 0100 0 14 3 27.0603 12.7211 0.8226 29.6605 0.2007 0 0 0.1138 0 0.1138 0100 0 14 4 24.9719 12.0514 0.83 29.9259 0.1896 0 0 0.1138 0 0.1138 0 1000 14 5 20.0669 11.3486 0.7334 26.4431 0.1416 0 0 0.1138 0 0.1138 0 100 014 6 19.3148 11.3116 0.7073 25.5033 0.128 0 0 0.1138 0 0.1138 0 100 0 147 13.0698 9.2496 0.5178 18.6703 0.0862 0 0 0.1138 0 0.1138 0 100 0 14 821.4825 14.0766 0.7634 27.5263 0.1153 0 0 0.1138 0 0.1138 0 100 0 14 923.8379 15.3459 0.8607 31.0347 0.1367 0 0 0.1138 0 0.1138 0 100 0 14 1021.5278 13.8928 0.7851 28.3081 0.1137 0 0 0.1138 0 0.1138 0 100 0 14 11−2.1621 −1.2165 −0.0091 −0.3271 −0.0078 0 0 0.1138 0 0.1138 0 100 0 1412 17.3041 11.5725 0.646 23.2923 0.0958 0 0 0.1138 0 0.1138 0 100 0 1413 1.949 2.0565 0.0896 3.2302 0.028 0 0 0.1138 0 0.1138 0 100 0 14 149.3689 6.5087 0.3449 12.4353 0.0636 0 0 0.1138 0.625 0.7388 0 15.4184.59 14 15 18.4324 12.0276 0.6914 24.9297 0.1067 0 0.625 0.1138 00.7388 84.59 15.41 0 14 16 −0.7558 −0.6898 0.0165 0.5934 0.0011 0 0 0 00 0 0 0 15 1 18.1472 11.9418 0.6987 25.1939 0.1082 0 0 0.1207 0 0.1207 0100 0 15 2 24.7631 13.6604 0.8641 31.1563 0.1697 0 0 0.1207 0 0.1207 0100 0 15 3 26.1211 11.8227 0.834 30.0705 0.2037 0 0 0.1207 0 0.1207 0100 0 15 4 24.5677 11.9552 0.7923 28.5692 0.1875 0 0 0.1207 0 0.1207 0100 0 15 5 20.0898 11.474 0.7193 25.9371 0.144 0 0 0.1207 0 0.1207 0 1000 15 6 19.3675 11.6613 0.6822 24.5972 0.1254 0 0 0.1207 0 0.1207 0 100 015 7 12.9911 8.3415 0.5124 18.477 0.0905 0 0 0.1207 0 0.1207 0 100 0 158 19.4851 12.9013 0.711 25.6353 0.1146 0 0 0.1207 0 0.1207 0 100 0 15 923.6077 14.5462 0.8618 31.074 0.1436 0 0 0.1207 0 0.1207 0 100 0 15 1021.2589 13.7735 0.7922 28.5624 0.1207 0 0 0.1207 0 0.1207 0 100 0 15 11−1.3789 −1.3203 0.0019 0.0686 −0.0106 0 0 0.1207 0 0.1207 0 100 0 15 1216.8366 10.3498 0.6489 23.3953 0.1014 0 0 0.1207 0 0.1207 0 100 0 15 132.5374 0.8067 0.138 4.9742 0.0357 0 0 0.1207 0 0.1207 0 100 0 15 1411.1396 7.0915 0.4088 14.741 0.0773 0 0 0.1207 0.625 0.7457 0 16.1883.82 15 15 17.5426 10.4944 0.7045 25.4019 0.1136 0 0.625 0.1207 00.7457 83.82 16.18 0 15 16 −0.4051 −0.4444 0.0729 2.6294 0.0112 0 0 0 00 0 0 0 16 1 15.0725 8.0994 0.5869 21.1613 0.0985 0 0 0.1275 0 0.1275 0100 0 16 2 24.67 8.6858 0.7009 25.2716 0.2051 0 0 0.1275 0 0.1275 0 1000 16 3 27.4278 6.3099 0.707 25.4923 0.2645 0 0 0.1275 0 0.1275 0 100 016 4 24.8032 6.1186 0.6967 25.1217 0.2372 0 0 0.1275 0 0.1275 0 100 0 165 20.9479 7.854 0.6707 24.1843 0.1784 0 0 0.1275 0 0.1275 0 100 0 16 619.4346 9.972 0.6893 24.8548 0.1408 0 0 0.1275 0 0.1275 0 100 0 16 714.3144 8.9315 0.5183 18.6864 0.0889 0 0 0.1275 0 0.1275 0 100 0 16 820.6449 13.6205 0.7023 25.3217 0.1142 0 0 0.1275 0 0.1275 0 100 0 16 924.2561 14.785 0.854 30.7919 0.1506 0 0 0.1275 0 0.1275 0 100 0 16 1021.0486 14.0733 0.6995 25.2209 0.1084 0 0 0.1275 0 0.1275 0 100 0 16 11−2.2759 −0.0846 0.0413 1.4879 0.024 0 0 0.1275 0 0.1275 0 100 0 16 1217.1423 10.7518 0.5869 21.1613 0.0898 0 0 0.1275 0 0.1275 0 100 0 16 133.0092 2.0883 0.2069 7.4586 0.0432 0 0 0.1275 0 0.1275 0 100 0 16 1412.8714 7.6083 0.5142 18.5415 0.1069 0 0 0.1275 0.625 0.7525 0 16.9483.06 16 15 17.5841 9.9481 0.6294 22.6946 0.129 0 0.625 0.1275 0 0.752583.06 16.94 0 16 16 25.0686 11.1805 0.8288 29.884 0.1822 0.1275 0 0 00.1275 0 100 0

What we claim is:
 1. A method for producing a hydrogen-rich gas whichcomprises: contacting a CO-containing gas with a water gas shiftcatalyst in the presence of water at a temperature of not more thanabout 450° C., wherein the water gas shift catalyst comprises: a) Pt,its oxides or mixtures thereof; b) at least one of Fe and Rh, theiroxides and mixtures thereof; and c) at least one member selected fromthe group consisting of Na, K, Sc, Y, Ti, Zr, V, Nb, Ta, Mo, Re, Co, Ni,Pd, Ge, Sn, Sb, La, Ce, Pr, Nd, Sm, and Eu, their oxides and mixturesthereof.
 2. A method according to claim 1, wherein the CO-containing gasis a syngas.
 3. A method according to claim 1, wherein the water gasshift catalyst comprises: a) Pt, its oxides or mixtures thereof; b) Rh,its oxides or mixtures thereof; and c) at least one member selected fromthe group consisting of Ti, Zr, Mo, Co, Ge, Sb, La and Ce, their oxidesand mixtures thereof.
 4. A method according to claim 3, wherein thewater gas shift catalyst comprises: a) Pt, its oxides or mixturesthereof; b) Rh, its oxides or mixtures thereof; and c) one or more of Geor Sb, their oxides and mixtures thereof.
 5. A method according to claim3, wherein the water gas shift catalyst comprises: Pt, its oxides ormixtures thereof; Rh, its oxides or mixtures thereof; and Mo, its oxidesand mixtures thereof.
 6. A method according to claim 3, wherein thewater gas shift catalyst comprises Pt, its oxides or mixtures thereof;Rh, its oxides or mixtures thereof; Co, its oxides or mixtures thereof,and one or more of La or Ce, their oxides and mixtures thereof.
 7. Amethod according to claim 3, wherein the water gas shift catalystcomprises Pt, its oxides or mixtures thereof; Rh, its oxides or mixturesthereof, and one or more of Ti, Zr, and Ce, their oxides and mixturesthereof.
 8. A method according to claim 1, wherein the water gas shiftcatalyst comprises: a) Pt, it oxides or mixtures thereof; b) Rh and Fe,their oxides and mixtures thereof; and c) at least one member selectedfrom the group consisting of Co, Pd, Ge, Sb, La, and Ce, their oxidesand mixtures thereof.
 9. A method according to claim 8, wherein thewater gas shift catalyst comprises Pt, its oxides or mixtures thereof;Rh, its oxides or mixtures thereof; Fe, its oxides or mixtures thereof,and one or more of Ge or Sb, their oxides and mixtures thereof.
 10. Amethod according to claim 8, wherein the water gas shift catalystcomprises Pt, its oxides or mixtures thereof; Rh, its oxides or mixturesthereof; Fe, its oxides or mixtures thereof, and one or more of Co, La,and Ce, their oxides and mixtures thereof.
 11. A method according toclaim 8, wherein the water gas shift catalyst comprises Pt, its oxidesor mixtures thereof; Rh, its oxides or mixtures thereof; Fe, its oxidesor mixtures thereof; and Pd, its oxides or mixtures thereof.
 12. Amethod according to claim 1, wherein the water gas shift catalyst issupported on a carrier comprising at least one member selected from thegroup consisting of alumina, zirconia, titania, ceria, magnesia,lanthania, niobia, zeolite, perovskite, silica clay, yttria and ironoxide and mixtures thereof.
 13. A method according to claim 12, whereinthe carrier comprises at least one member selected from the groupconsisting of zirconia, titania and ceria.
 14. A method according toclaim 13, wherein the carrier comprises zirconia.
 15. A method accordingto claim 1, wherein the CO-containing gas is contacted with the watergas shift catalyst at a temperature ranging from about 150° C. to about450° C.
 16. A method according to claim 15, wherein the CO-containinggas is contacted with a water gas shift catalyst at a temperatureranging from about 350° C. to up to about 450° C.
 17. A method accordingto claim 15, wherein the CO-containing gas is contacted with the watergas shift catalyst at a temperature ranging from about 250° C. to up toabout 350° C.
 18. A method according to claim 15, wherein theCO-containing gas is contacted with a water gas shift catalyst at atemperature ranging from about 150° C. to up to about 250° C.
 19. Amethod according to claim 1, wherein the CO-containing gas is contactedwith the water gas shift catalyst at a pressure of no more than about 75bar.
 20. A method according to claim 19, wherein the CO-containing gasis contacted with the water gas shift catalyst at a pressure of no morethan about 50 bar.
 21. A method according to claim 19, wherein theCO-containing gas is contacted with the water gas shift catalyst at apressure of no more than about 25 bar.
 22. A method according to claim19, wherein the CO-containing gas is contacted with the water gas shiftcatalyst at a pressure of no more than about 15 bar.
 23. A methodaccording to claim 19, wherein the CO-containing gas is contacted withthe water gas shift catalyst at a pressure of no more than about 1 bar.24. A method according to claim 1, wherein the water gas shift catalystcomprises between about 0.01 wt. % to about 10 wt. %, with respect tothe total weight of all catalyst components plus the support material,of each Group 8, 9, or 10 element present in the water gas shiftcatalyst.
 25. A method according to claim 24, wherein the water gasshift catalyst comprises between about 0.01 wt. % to about 2 wt. % ofeach Group 8, 9, or 10 element present in the water gas shift catalyst.26. A method according to claim 25, wherein the water gas shift catalystcomprises between about 0.05 wt. % to about 0.5 wt. % of each Group 8,9, or 10 element present in the water gas shift catalyst.
 27. A watergas shift catalyst comprising: a) Pt, its oxides or mixtures thereof; b)at least one of Fe and Rh, their oxides and mixtures thereof; and c) atleast one member selected from the group consisting of Na, K, Sc, Y, Ti,Zr, V, Nb, Ta, Mo, Re, Co, Ni, Pd, Ge, Sn, Sb, La, Ce, Pr, Nd, Sm, andEu, their oxides and mixtures thereof.
 28. A water gas shift catalystaccording to claim 27, wherein the water gas shift catalyst comprises:a) Pt, its oxides or mixtures thereof; b) Rh, its oxides or mixturesthereof; and c) at least one member selected from the group consistingof Ti, Zr, Mo, Co, Ge, Sb, La and Ce, their oxides and mixtures thereof.29. A water gas shift catalyst according to claim 28, wherein the watergas shift catalyst comprises: a) Pt, its oxides or mixtures thereof; b)Rh, its oxides or mixtures thereof; and c) one or more of Ge or Sb, itsoxides and mixtures thereof.
 30. A water gas shift catalyst according toclaim 28, wherein the water gas shift catalyst comprises: Pt, its oxidesor mixtures thereof; Rh, its oxides or mixtures thereof; and Mo, itsoxides or mixtures thereof.
 31. A water gas shift catalyst according toclaim 28, wherein the water gas shift catalyst comprises Pt, its oxidesor mixtures thereof; Rh, its oxides or mixtures thereof; Co, its oxidesor mixtures thereof, and one or more of La or Ce, their oxides andmixtures thereof.
 32. A water gas shift catalyst according to claim 28,wherein the water gas shift catalyst comprises Pt, its oxides ormixtures thereof; Rh, its oxides or mixtures thereof, and one or more ofTi, Zr, and Ce, their oxides and mixtures thereof.
 33. A water gas shiftcatalyst according to claim 27, wherein the water gas shift catalystcomprises: a) Pt, it oxides or mixtures thereof; b) Rh and Fe, theiroxides and mixtures thereof; and. c) at least one member selected fromthe group consisting of Co, Pd, Ge, Sb, La, and Ce, their oxides andmixtures thereof.
 34. A water gas shift catalyst according to claim 33,wherein the water gas shift catalyst comprises Pt, its oxides ormixtures thereof; Rh, its oxides or mixtures thereof; Fe, its oxides ormixtures thereof, and one or more of Ge or Sb, their oxides and mixturesthereof.
 35. A water gas shift catalyst according to claim 33, whereinthe water gas shift catalyst comprises Pt, its oxides or mixturesthereof; Rh, its oxides or mixtures thereof; Fe, its oxides or mixturesthereof, and one or more of Co, La, and Ce, their oxides and mixturesthereof.
 36. A water gas shift catalyst according to claim 33, whereinthe water gas shift catalyst comprises Pt, its oxides or mixturesthereof; Rh, its oxides or mixtures thereof; Fe, its oxides or mixturesthereof; and Pd, its oxides or mixtures thereof.
 37. A water gas shiftcatalyst according to claim 27, wherein the water gas shift catalyst issupported on a carrier comprising at least one member selected from thegroup consisting of alumina, zirconia, titania, ceria, magnesia,lanthania, niobia, zeolite, perovskite, silica clay, yttria and ironoxide and mixtures thereof.
 38. A water gas shift catalyst according toclaim 37, wherein the carrier comprises at least one member selectedfrom the group consisting of zirconia, titania and ceria.
 39. A watergas shift catalyst according to claim 38, wherein the carrier compriseszirconia.
 40. A water gas shift catalyst according to claim 27, whereinthe water gas shift catalyst comprises between about 0.01 wt. % to about10 wt. %, with respect to the total weight of all catalyst componentsplus the support material, of each Group 8, 9, or 10 element present inthe water gas shift catalyst.
 41. A water gas shift catalyst accordingto claim 40, wherein the water gas shift catalyst comprises betweenabout 0.01 wt. % to about 2 wt. %, of each Group 8, 9, or 10 elementpresent in the water gas shift catalyst.
 42. A water gas shift catalystaccording to claim 41, wherein the water gas shift catalyst comprisesbetween about 0.05 wt. % to about 0.5 wt. % of each Group 8, 9, or 10element present in the water gas shift catalyst.
 43. A fuel processingsystem for generation of a hydrogen-rich gas from a hydrocarbon orsubstituted hydrocarbon fuel, the fuel processing system comprising afuel reformer for converting a fuel reactant stream comprising ahydrocarbon or a substituted hydrocarbon fuel to a reformed productstream comprising carbon monoxide and water, the fuel reformer having aninlet for receiving the reactant stream, a reaction chamber forconverting the reactant stream to the product stream, and an outlet fordischarging the product stream, a water gas shift reactor for effectinga water gas shift reaction at a temperature of less than about 450° C.,the water gas shift reactor comprising an inlet for receiving a watergas shift feed stream comprising carbon monoxide and water from theproduct stream of the fuel reformer, a reaction chamber comprising awater gas shift catalyst selected from any one of the catalysts of claim27, the water gas shift catalyst being effective for generating hydrogenand carbon dioxide from the water gas shift feed stream, and an outletfor discharging the resulting hydrogen-rich gas, and a temperaturecontroller adapted for maintaining the temperature of the reactionchamber of the water gas shift reactor at a temperature of less thanabout 450° C.